CN102806087B - Ni-La-B (nickel-lanthanum-boron) catalyst as well as preparation method of Ni-La-B catalyst and application of Ni-La-B catalyst to hydrogen preparation through hydroboron alcoholysis - Google Patents
Ni-La-B (nickel-lanthanum-boron) catalyst as well as preparation method of Ni-La-B catalyst and application of Ni-La-B catalyst to hydrogen preparation through hydroboron alcoholysis Download PDFInfo
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- CN102806087B CN102806087B CN201210308908.XA CN201210308908A CN102806087B CN 102806087 B CN102806087 B CN 102806087B CN 201210308908 A CN201210308908 A CN 201210308908A CN 102806087 B CN102806087 B CN 102806087B
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Abstract
The invention provides a Ni-La-B (nickel-lanthanum-boron) catalyst as well as a preparation method of the Ni-La-B catalyst and application of the Ni-La-B catalyst to hydrogen preparation through hydroboron alcoholysis. A catalytic reduction method is adopted for synthesizing the catalyst, weighed Ni salt and La salt are subjected to ultrasonic dissolution into deionized water, during the ultrasonic treatment, KBH4 solution is added into the Ni salt and La salt solution drip by drip, the catalyst is reduced, the catalyst solution which is sufficiently reduced is placed into a vacuum drying box to be dried, the Ni-La-B catalyst is obtained, and protection gas is used in the reduction process so that the catalyst is prevented from being oxidized by oxygen. The Ni-La-B catalyst prepared by the invention has excellent catalysis effects and circulation activity, the level is similar to that of noble metal catalysts, and in addition, the cost is low. The Ni-La-B catalyst, the preparation method and the application also have the advantages that the operation is simple and convenient, the process and the equipment are simple, no pollution is caused on environment, the recovery utilization times are many, the cost is low, and the like. Great industrial use prospects are realized.
Description
Technical field
The invention belongs to portable hydrogen technical field, be specifically related to a kind of Ni-La-B Catalysts and its preparation method and the application in boron hydride alcoholysis hydrogen manufacturing.
Background technology
A large amount of exploitations and the use of traditional energy, caused serious energy crisis and environmental pollution, brought serious problems to socioeconomic sustainable development and the mankind's existence.It is particularly important that the exploitation of new forms of energy seems, comprises solar energy, wind energy, biological energy source, Hydrogen Energy, ocean energy and geothermal energy etc.Wherein hydrogen is desirable energy carrier, only produces water during burning, does not produce any pollutant.The energy substance traditional with other compared, and also has the plurality of advantages such as energy density is high, thermal transition efficiency height.
Potassium borohydride hydrolytic hydrogen production has all been proved to be a kind of safety, Chu Qing and has led highly, and eco-friendly feasible hydrogen source technology, is a kind of convenience, practicality and the novel hydrogen generation technique that can effectively prepare high-purity hydrogen.Compare with other storage hydrogen modes, the advantage of potassium borohydride catalyzing hydrolysis hydrogen manufacturing is: (1) high storage hydrogen efficiency.(2) produce gentle (3) hydrogen manufacturing purity high (4) handling safety of hydrogen condition, without environment negative effect, hydrolysising by-product KBO
2the recycling of can rolling off the production line.Above-mentioned technological merit has determined KBH
4catalyzing hydrolysis hydrogen generating system technology has a good application prospect.
Work as KBH
4disengage with catalyst, hydrolysis can stop at once, so H-H reaction is produced in its hydrolysis, has good controllability.
But potassium borohydride hydrolytic hydrogen production comes with some shortcomings, comprising the accessory substance inhibition problem of potassium borohydride hydrolysis, water existed with the phase of solution in subzero being difficult to.This just needs a kind of new reaction dissolvent to optimize it.The part similitude of the chemical constitution of ethanol and water and physical property aspect can replace water to be used as reaction dissolvent, and the low freezing point of ethanol can carry out potassium borohydride hydrogen production reaction below zero degrees celsius.
But it is very slow that potassium borohydride alcoholysis is reacted at low temperatures, product hydrogen rate is low, is difficult to realize application at low temperatures.Therefore, find make at low temperatures potassium borohydride alcoholysis hydrogen production reaction can be efficiently, catalyst lasting, that stably carry out becomes the key that fuel cell is applied under low temperature environment.
Research finds that most catalyst can be used for the hydrogen manufacturing of catalyzed alcoholysis sodium borohydride.Pt(Kojima is found in research, 2002,1029), Ru(Amendolat, 2000,969) etc. the excellent catalytic effect of noble metal catalyst, can provide efficient hydrogen to prepare speed, but cost is high and easily the drawbacks limit such as inactivation its application.
Common metal is applied to the alcoholysis of catalysis potassium borohydride and prepares hydrogen as Co and Ni etc. is widely studied, as Ni-B/TiO2 (J.HanKuer, 2011,3) Co-Ni-B(Suresh Babu Kalidindi, 2008,770) etc., but it is active and stability is not ideal enough.The activity of catalyst and stability are the important indicators of evaluate catalysts quality.
Summary of the invention
The above-mentioned defect existing for potassium borohydride alcoholysis hydrogen manufacturing used catalyst in prior art, order of the present invention is to provide a kind of Ni-La-B Catalysts and its preparation method and the application in boron hydride alcoholysis hydrogen manufacturing, catalyst cost of the present invention is low, described preparation method is easy, and hydrogen-producing speed is high.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
A Ni-La-B catalyst, described catalyst activity component is Ni-La-B crystal particle, specific area is 200-500m
2/ g, the quality percentage composition of B in Ni-La-B crystal particle is 5-15%, the mol ratio of Ni and La is 1:10-10:1.
The preparation method of the Ni-La-B catalyst described in the present invention also provides, it comprises the following steps:
Prepare respectively nickel salt and lanthanum saline solution that mass percent concentration is 1%-85%, be placed on ultrasonic 1 ~ 5h in ultrasonic cleaner; Taking potassium borohydride adds water and makes it to dissolve, (nickel salt+lanthanum salt): the mol ratio of potassium borohydride is 1:5-0.5:1, solution of potassium borohydride is dropwise joined in nickel salt and lanthanum salting liquid, catalyst is reduced, in reduction process, with protection gas, make catalyst avoid dioxygen oxidation; By the sufficient catalyst of reduction be dried, grind, sieve, standby.
Further improvement to technique scheme: described nickel salt is a kind of in nickel nitrate, nickelous sulfate, nickelous carbonate or nickel chloride, described lanthanum salt is a kind of in lanthanum nitrate, lanthanum sulfate, lanthanum carbonate or lanthanum chloride.
Further improvement to technique scheme: described boron hydride is sodium borohydride, potassium borohydride, lithium borohydride, calcium borohydride or hydroboration barium.
Further improvement to technique scheme: described is nitrogen for the protection of gas.
Further improvement to technique scheme: described drying condition is for being 60 ~ 100 ℃ in vacuum drying chamber temperature, and be 1 ~ 16h drying time.
Ni-La-B catalyst described in the present invention also provides is in the application for potassium borohydride alcoholysis hydrogen manufacturing.
Further improvement to technique scheme: described Ni-La-B catalyst can be recycled more than 20 times.
Further improvement to technique scheme: use described catalyst in the time of 0-40 ℃, raise with temperature, reaction rate accelerates.
Compared with prior art, advantage of the present invention and good effect are:
1, the present invention is by adopting metal Ni and the co-catalyst La of high catalytic activity to prepare Ni-La-B catalyst, precious metals pd and Pt have been replaced, reduced catalyst cost, the catalytic activity of this catalyst approaches the catalytic effect of noble metal, but but a lot of than noble metal cost, there is great industrial application value.
2, the present invention does not use inert carrier, relies on easy chemical reduction method can prepare Ni-La allomeric catalyst granules, and particle size distribution is homogeneous comparatively, and catalytic activity is high.
3, the present invention also has that easy and simple to handle, technology and equipment is simple, environmentally safe, recoverable (be greater than 20 times) and low cost and other advantages often.
Read by reference to the accompanying drawings after the specific embodiment of the present invention, it is clearer that the other features and advantages of the invention will become.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the Ni-La-B catalyst of preparation in the embodiment of the present invention 1.
Fig. 2 is the electron scanning micrograph of the Ni-La-B catalyst of preparation in the embodiment of the present invention 2.
Fig. 3 is the kinetic curve figure that in the embodiment of the present invention 3, under different temperatures, hydrogen generates
Fig. 4 is that the hydrogen of the Ni-La-B catalyst differential responses number of times of preparation in the embodiment of the present invention 4 generates kinetic curve figure.
Fig. 5 is the electron scanning micrograph of 20 circular response rear catalysts in the embodiment of the present invention 4.
Fig. 6 is the product hydrogen design sketch that uses different quality Ni-La-B catalyst in the embodiment of the present invention 5.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in further detail.
The present invention is raw materials used is: lanthanum nitrate hexahydrate particle (analyzing pure); Potassium borohydride particle (analyzing pure); Six water nickel nitrate particles (analyzing pure); Nickel sulfate hexahydrate (analyzing pure); Six water lanthanum chlorides (analyzing pure).
Embodiment 1
Six water nickel nitrates and 1.3g lanthanum nitrate hexahydrate by 2.0g, add 10ml deionized water dissolving, and preparation molar concentration is 0.7mol/l nickel salt and 0.3mol/l lanthanum salting liquid.First be placed on ultrasonic cleaner and carry out ultrasonic dispersion 1h, then in ultrasonic at N
2atmosphere under by the KBH of 1mol/l
4solution is dropwise added drop-wise in described nickel salt and lanthanum salting liquid, by Ni
2+and La
3+be reduced to simple substance Ni and simple substance La, and form amorphous Ni-La-B catalyst with element B.Solution after reduction is put into vacuum drying chamber dry 10h under 90 ℃ of conditions, by grinding, sieve, seal up for safekeeping standby.The electromicroscopic photograph (SEM) of the Ni-La-B catalyst that the present embodiment makes as shown in Figure 1.As seen from Figure 1, Ni-La-B catalyst granules particle diameter approximately 100 nm that prepare, and reunite together.It is 228.5m that BET characterizes specific area
2/ g.
Embodiment 2
By the nickel sulfate hexahydrate of 1.83g and 1.1g six water lanthanum chlorides, add 20ml deionized water dissolving, preparation molar concentration is 0.35mol/l nickel salt and 0.15mol/l lanthanum salting liquid.First be placed on ultrasonic cleaner and carry out ultrasonic dispersion 2h, then in ultrasonic at N
2atmosphere under by the KBH of 2mol/l
4solution is dropwise added drop-wise in the solution that fills nickel salt and lanthanum salt, by Ni
2+and La
3+be reduced to simple substance Ni and simple substance La, and form amorphous Ni-La-B catalyst with element B.Solution after reduction is put into vacuum drying chamber dry, by grinding, sieve, seal up for safekeeping standby.The electromicroscopic photograph (SEM) of the Ni-La-B catalyst that the present embodiment makes as shown in Figure 2.As seen from Figure 2, the Ni-La-B catalyst granules preparing is larger than the catalyst granules particle diameter in Fig. 1, particle diameter approximately 400 nm, agglomeration not as in Fig. 1 significantly.
Embodiment 3
The preparation method of catalyst as described in Example 1, with 10wt.% KBH
4+ 8wt.%NaOH is reactant liquor, gets the described Ni-La-B catalyst of 0.075g through grinding, with KBH described in 10mL
4+ NaOH reactant liquor, is controlled at bath temperature respectively 0 ℃, 15 ℃, 25 ℃, 35 ℃, 40 ℃ and reacts, Yin Wendu differential responses asynchronism(-nization).As shown in Figure 3, as can be seen from Figure 3, along with the rising of temperature, the reaction time shortens the kinetic curve that under different temperatures, hydrogen generates gradually, and reaction rate is accelerated gradually.Temperature rises to 17 minutes 40 ℃ of reaction time from 0 ℃ and shortens to 4.5 minutes.
Embodiment 4
The preparation method of catalyst as described in Example 1, with 10wt.% KBH
4+ 8wt.%NaOH is reactant liquor, gets the described Ni-La-B catalyst of 0.075g through grinding, with KBH described in 10mL
4+ NaOH reactant liquor reacts under 25 ℃ of bath temperatures, and catalyst activity is along with increasing gradually of access times reduces.Catalyst is repeated to recycle 20 times, and the hydrogen of differential responses number of times generates kinetic curve as shown in Figure 4.Fig. 4 shows that catalyst that the present embodiment makes is at the hydrogen production efficiency figure of 20 circular responses, and under the identical prerequisite of hydrogen output, the activity of catalyst reduces gradually, and the reaction time of the 1st time is the shortest, and the 2-10 secondary response time is close, and cycle performance is good.Fig. 5 shows catalyst that the present embodiment the makes electromicroscopic photograph after 20 circular responses.Fig. 5 and Fig. 1 contrast can obtain, and the structure of catalyst does not change substantially, still has good catalytic activity.
Embodiment 5
The preparation method of catalyst as described in Example 2, with 10wt.% KBH
4+ 8wt.%NaOH is reactant liquor, and getting catalyst amount is 0.0375g, 0.0750g, 0.1125g, reacts under 25 ℃ of bath temperatures with reactant liquor described in 10mL, and catalyst use amount is more, and the catalyzing manufacturing of hydrogen time is shorter.The hydrogen of different catalysts consumption generates kinetic curve as shown in Figure 6.This result shows, catalyst amount is larger, and catalytic effect is better, but consumption is while being 0.1125g, and the reaction time is 4.5min, and this reaction effect approaches the catalytic effect of noble metal.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (6)
1. a Ni-La-B catalyst, is characterized in that described catalyst activity component is Ni-La-B crystal particle, and specific area is 200-500m
2/ g, the quality percentage composition of B in Ni-La-B crystal particle is 5-15%, the mol ratio of Ni and La is 1:10-10:1,
The preparation method of described Ni-La-B catalyst is: prepare respectively nickel salt and lanthanum saline solution that mass percent concentration is 1%-85%, be placed on ultrasonic 1 ~ 5h in ultrasonic cleaner; Taking potassium borohydride adds water and makes it to dissolve, nickel salt+lanthanum salt: the mol ratio of potassium borohydride is 1:5-0.5:1, solution of potassium borohydride is dropwise joined in nickel salt and lanthanum salting liquid, catalyst is reduced, in reduction process, with nitrogen, make catalyst avoid dioxygen oxidation; By the sufficient catalyst of reduction vacuum drying chamber temperature be 60 ~ 100 ℃ dry, be 1 ~ 16h drying time, grind, sieve, standby.
2. the preparation method of a kind of Ni-La-B catalyst according to claim 1, is characterized in that it comprises the following steps: prepare respectively nickel salt and lanthanum saline solution that mass percent concentration is 1%-85%, be placed on ultrasonic 1 ~ 5h in ultrasonic cleaner; Taking potassium borohydride adds water and makes it to dissolve, nickel salt+lanthanum salt: the mol ratio of potassium borohydride is 1:5-0.5:1, solution of potassium borohydride is dropwise joined in nickel salt and lanthanum salting liquid, catalyst is reduced, in reduction process, with nitrogen, make catalyst avoid dioxygen oxidation; By the sufficient catalyst of reduction vacuum drying chamber temperature be 60 ~ 100 ℃ dry, be 1 ~ 16h drying time, grind, sieve, standby.
3. the preparation method of Ni-La-B catalyst according to claim 2, is characterized in that: described nickel salt is a kind of in nickel nitrate, nickelous sulfate, nickelous carbonate or nickel chloride, and described lanthanum salt is a kind of in lanthanum nitrate, lanthanum sulfate, lanthanum carbonate or lanthanum chloride.
4. Ni-La-B catalyst according to claim 1 is in the application for potassium borohydride alcoholysis hydrogen manufacturing.
5. Ni-La-B catalyst according to claim 4, in the application for potassium borohydride alcoholysis hydrogen manufacturing, is characterized in that: described Ni-La-B catalyst can be recycled more than 20 times.
6. Ni-La-B catalyst according to claim 4, in the application for potassium borohydride alcoholysis hydrogen manufacturing, is characterized in that: use described catalyst in the time of 0-40 ℃, with temperature, raise, reaction rate accelerates.
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