CN104925751A - Preparing method for improving LiH-NH<3> hydrogen storing system dehydrogenizing kinetics - Google Patents

Preparing method for improving LiH-NH<3> hydrogen storing system dehydrogenizing kinetics Download PDF

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CN104925751A
CN104925751A CN201510339530.3A CN201510339530A CN104925751A CN 104925751 A CN104925751 A CN 104925751A CN 201510339530 A CN201510339530 A CN 201510339530A CN 104925751 A CN104925751 A CN 104925751A
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lih
hydrogen
reaction
linh
amides
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滕云雷
董宝霞
陈林婷
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Yangzhou University
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Yangzhou University
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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
    • Y02E60/32—Hydrogen storage

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Abstract

The invention provides a preparing method for improving LiH-NH3 hydrogen storing system dehydrogenizing kinetics, and belongs to the technical field of solid state chemistry hydrogen storing. The method comprises the following steps that under the condition of hydrogen, after pre-ball-milling is carried out on alkali metal amides, the alkali metal amides are mixed with LiH, ball-milling treatment is carried out, and LiH materials adulterating with the alkali metal amides are obtained; under the condition without oxygen, hydrogen evolution reaction is carried out on the LiH materials adulterating with the alkali metal amides and the hydrogen, cooling is carried out after the reaction is finished, LiH-NH3 which improves the hydrogen storing system dehydrogenizing kinetics is obtained. Due to the fact that adulterating LiNH2 has the crystal nucleus function in the process that the LiH and NH3 are reacted to generated LiNH2 and H2, the hydrogen evolution reaction is accelerated to carry out, and the LiH-NH3 system dehydrogenizing kinetics can be effectively improved.

Description

One improves LiH – NH 3the dynamic (dynamical) preparation method of hydrogen storage system dehydrogenation
Technical field
The invention belongs to solid state chemistry hydrogen storage technology field, particularly seed effect improves LiH – NH 3the dynamic (dynamical) preparation method of (lithium hydride-ammonia) hydrogen storage system dehydrogenation.
Background technology
In Sustainable development and friendly environment society, searching one cleans and the high-octane energy is even more important.Because hydrogen only produces water after combustion with air, so become the most attracting no pollution energy.Although as lightweight element hydrogen rich reserves and there is high-energy-density, the extensive utilization of Hydrogen Energy and be subject to the restriction of storing up hydrogen mode.Two kinds of traditional storage hydrogen modes, also because having lower volume density, are difficult to the practical application realizing vehicle-mounted storage hydrogen.And the appearance of solid-state hydrogen storage technology, improve current situation.Special in lightweight element hydrogen storage system, the solid-state safety achieving high weight and high volume density stores up hydrogen.
Have metal hydrogen storage, carbonaceous material hydrogen storage method etc. for solid-state storage hydrogen, but experiment proves the needs that can not meet the vehicle-mounted storage hydrogen of business well.Therefore, people start to turn to research some light-weight metal, such as alkali metal lithium, the compound of sodium or potassium.Ammonia has the higher hydrogen storage capability that can reach 17.8 mass%, and easily compresses and liquefies in a mild condition, becomes welcome hydrogen carrier.But make ammonia decomposing hydrogen-production need suitable catalyzer and the high temperature higher than 400 DEG C, the harshness of condition limits the practical application of ammonia storage hydrogen.But relevant report is introduced, and alkalimetal hydride can obtain a kind of reversible hydrogen storage material with ammonia react, and reaction equation is as follows: MH+NH 3→ MNH 2+ H 2(wherein, M is Li or Na or K).Further, utilize the rapid reaction of alkalimetal hydride and ammonia, Metal-N-H hydrogen storage material can be eliminated and put the by product NH generated in hydrogen process 3, NH 3electrode catalyst of fuel cell can be caused poisoning.In above-mentioned three kinds of systems, LiH – NH 3system has the most high hydrogen storage reaching 8.1 wt%, and owing to being the thermopositive reaction of similar hydrolyzed type, so just can dehydrogenation reaction be carried out at relatively low temperature.But the slower reaction kinetics of this system hinders practical application.
In order to improve LiH – NH 3the hydrogen desorption kinetics of system, existing people's research adds Ti and relevant potassium compound such as KH in this Li – N – H system, KX(wherein X is F, Cl or Br) etc., find that the suction/hydrogen desorption kinetics performance of adding for improving Li – N – H system has good catalytic effect, significantly can improve LiH – NH 3the dynamic performance of hydrogen is put in the suction of system.
Summary of the invention
The object of the invention is to propose the simple and operational safety of a kind of equipment requirements, and LiH – NH can be improved 3the method of the suction hydrogen desorption kinetics performance of system.
The present invention includes following steps:
1) under an atmosphere of hydrogen, carrying out ball-milling processing by mixing with LiH after pre-for alkali metal amino compound ball milling, obtaining the LiH material of alkali doped amides;
2) in the absence of oxygen, expected by the LiH of alkali doped amides to carry out hydrogen discharge reaction with ammonia, reaction terminates rear cooling, obtains and improves the dynamic (dynamical) LiH-NH of hydrogen storage system dehydrogenation 3.
In a hydrogen atmosphere, ball-milling processing obtains the doped crystal particle that size can reach Nano grade in the present invention, and alkali doped amides can be distributed in LiH sample better.Meanwhile, due to the LiNH of doping 2at LiH and NH 3reaction generates LiNH 2and H 2play the effect of nucleus in process, thus accelerate the carrying out of hydrogen discharge reaction, LiH – NH can be effectively improved 3the dehydrogenation kinetics of system.
Further, alkali metal amino compound of the present invention is LiNH 2.The experiment proved that, LiNH 2, NaNH 2and KNH 2to LiH – NH 3the dehydrogenation productive rate of system is all improved.But, LiNH 2doping best results.At 100 DEG C, under 1h reaction conditions, productive rate can be made to improve 6.5%.
LiNH described in the LiH material of alkali doped amides 2doping be 0.5 ~ 3mol%.Different doping is to LiH – NH after deliberation 3the impact of system dehydrogenation productive rate, finds to work as LiNH 2doping within the scope of 0.5 ~ 3mol%, LiNH 2doping dehydrogenation productive rate can be made to improve 1.3-6.5%, and along with the increase of doping, reaction yield presents the trend first increasing and subtract afterwards.
More preferably LiNH described in the LiH material of alkali doped amides 2doping be 1mol%, greatly can improve reaction yield, reach 45%.Can find out from XRD figure, 0.5mol% LiNH 2doping because of content less, there is not obvious LiNH 2characteristic peak, and work as LiNH 2doping just can reach the samples contg requirement of XRD analysis when being increased to 1mol%.
Described step 2) in, alkali doped amides is first placed in stainless steel tube, after emptying described stainless steel inner air tube, then passes into 0.5 MPa ammonia and carry out hydrogen discharge reaction.Because LiH is oxidizable in atmosphere, so need react under anaerobic.In addition, consider the finite volume of stainless steel tube, meet LiH and NH 3the amount of reaction, than when for 1:1, ensures that the solid sample quality claimed is in the limit of error allowed, so select to be filled with 0.5 MPa ammonia.
Described step 2) in, the temperature condition of described hydrogen discharge reaction is 100 DEG C, and the reaction times is 1 hour.Fuel cell is higher for temperature requirement, when temperature is higher than 100 DEG C, then inapplicable.So LiH – NH 3system is put hydrogen and need be carried out at low temperatures, and the temperature condition selecting hydrogen discharge reaction is 100 DEG C.Simultaneously the selective reaction time is 1 hour, is because speed of reaction is very fast in this system 1 hour.
Accompanying drawing explanation
Fig. 1 is Different L iNH 2the X-ray diffractogram of LiH sample after ball-milling processing of doping.
Fig. 2 is Different L iNH 2doping LiH sample and plain LiH respectively with the ammonia gas react productive rate comparison diagram of 1 hour.
Fig. 3 is 1 mol% LiNH of step 3) of the present invention 2doping sample and LiH sample under uniform temp and time with the productive rate comparison diagram of ammonia gas react.
Fig. 4 is doping 1 mol% LiNH 2liH sample and the productive rate comparison diagram that reacts at 75 DEG C and 100 DEG C of ammonia.
Fig. 5 is doping 1 mol% LiNH 2liH sample and the average yield comparison diagram of ammonia under 100 DEG C of differential responses time.
Embodiment
One, embodiment 1:
1, ball milling LiH sample: in vacuum glove box, takes 0.3g LiH crystal prototype and loads in the ball grinder containing 30 stainless steel steel balls.Then from glove box, take out ball grinder, be filled with a certain amount of hydrogen, and ball grinder symmetry is installed in planetary ball mill, ball-milling processing 2 hours under the rotating speed of 350 revs/min.
2, sampling and ammonia carry out hydrogen discharge reaction: in vacuum glove box, accurately take 0.0191gLiH crystal prototype in stainless steel heating tube, and stainless steel heating tube is installed in reaction unit, after gas circuit being vacuumized and gets rid of air residual in gas circuit, the temperature controller parameter to 100 DEG C of setting reaction.
After reaching design temperature in reactor to be heated, be filled with rapidly 0.5MPa ammonia, react 1 hour, stop experiment, and the gas immediately in blowdown piping, treat that stainless steel heating tube is cooled to room temperature, take out reacted samples weighing and record dehydrogenation reaction productive rate.
3, the independent hydrogen discharge reaction that carries out with ammonia respectively of the biased sample of research doping best results and LiH sample: with reference to the method for above step 2, under the temperature of reaction condition of 100 DEG C, carry out the experiment of 2,4,6 and 12 hours differential responses time respectively; Then, be all under the condition of 1 little time in the reaction times, carry out the reaction experiment that temperature of reaction condition is 75,150 and 200 DEG C respectively.
After recording each test respectively, stainless steel heating tube is cooled to room temperature, takes out reacted sample weight and record dehydrogenation reaction productive rate respectively.
Two, embodiment 2:
1, ball milling doping 0.5mol% LiNH 2liH sample: first to the LiNH for adulterating 2sample is with the rotating speed ball milling pretreatment 24 hours of 450 revs/min.Then, in vacuum glove box, 0.2957g LiH and 0.0043g LiNH is taken 2sample loads in the ball grinder containing 30 stainless steel steel balls.From glove box, take out ball grinder again, be filled with a certain amount of hydrogen, and ball grinder symmetry is installed in planetary ball mill, ball-milling processing 2 hours under the rotating speed of 350 revs/min.
2, sampling and ammonia carry out hydrogen discharge reaction: in vacuum glove box, accurately take 0.0194g above-mentioned doping 0.5mol% LiNH 2liH in stainless steel heating tube, and stainless steel heating tube is installed in reaction unit, after gas circuit being vacuumized and gets rid of air residual in gas circuit, the temperature controller parameter to 100 DEG C of setting reaction.
To be heated to design temperature 100 DEG C, be filled with rapidly 0.5 MPa ammonia, react 1 hour, stop testing, and the gas immediately in blowdown piping, treat that stainless steel heating tube is cooled to room temperature, take out reacted samples weighing and record dehydrogenation reaction productive rate.
Three, embodiment 3:
1, ball milling adulterates 1 mol% LiNH 2liH sample: in vacuum glove box, take 0.2913 g LiH and 0.0087 g LiNH 2sample (through ball milling pretreatment) loads in the ball grinder containing 30 stainless steel steel balls.Then from glove box, take out ball grinder, be filled with a certain amount of hydrogen, and ball grinder symmetry is installed in QM-3SP4 planetary ball mill, under the rotating speed of 350 revs/min, ball milling 2 hours.
2, sampling and ammonia carry out hydrogen discharge reaction: in vacuum glove box, accurately take the above-mentioned doped samples of 0.0197 g in stainless steel heating tube, and stainless steel heating tube is installed in reaction unit, the air inlet path of first cleaning reaction device, after gas circuit being vacuumized and gets rid of air residual in gas circuit, the temperature controller parameter to 100 DEG C of setting reaction.
To be heated to design temperature 100 DEG C, be filled with rapidly 0.5 MPa ammonia, react 1 hour, stop testing.And the gas immediately in blowdown piping, treat that stainless steel heating tube is cooled to room temperature, take out reacted samples weighing and record dehydrogenation reaction productive rate.
3, the independent hydrogen discharge reaction that carries out with ammonia respectively with LiH sample of the biased sample of research doping best results: with reference to described in (2), at 100 DEG C, do for supplement the experiment of reacting different time, react 2,4,6 and 12 hours respectively; Then, at differing temps 75,150 and 200 DEG C, do for supplement the experiment of reacting respectively 1 hour.
Four, embodiment 4:
1, ball milling adulterates 2 mol% LiNH 2liH sample: in vacuum glove box, take 0.2836 g LiH and the 0.0164 g LiNH through ball milling pretreatment 2load in the ball grinder containing 30 stainless steel steel balls.Then from glove box, take out ball grinder, be filled with a certain amount of hydrogen, and ball grinder symmetry is installed in planetary ball mill, under the rotating speed of 350 revs/min, ball milling 2 hours.
2, sampling and ammonia carry out hydrogen discharge reaction: in vacuum glove box, accurately take 0.0203 g above-mentioned doping 2 mol% LiNH 2liH sample in stainless steel heating tube, and stainless steel heating tube is installed in reaction unit, after gas circuit being vacuumized and gets rid of air residual in gas circuit, the temperature controller parameter to 100 DEG C of setting reaction.
To be heated to design temperature 100 DEG C, be filled with rapidly 0.5MPa ammonia, react 1 hour, stop testing, and the gas immediately in blowdown piping, treat that stainless steel heating tube is cooled to room temperature, take out reacted samples weighing and record dehydrogenation reaction productive rate.
Five, embodiment 5:
1, ball milling adulterates 3 mol% LiNH 2liH sample: in vacuum glove box, take 0.2761 g LiH and the 0.0239 g LiNH through ball milling pretreatment 2load in the ball grinder containing 30 stainless steel steel balls.Then from glove box, take out ball grinder, be filled with a certain amount of hydrogen, and ball grinder symmetry is installed in planetary ball mill, under the rotating speed of 350 revs/min, ball milling 2 hours.
2, sampling and ammonia carry out hydrogen discharge reaction: in vacuum glove box, accurately take 0.0208 g above-mentioned doping 3 mol% LiNH 2the sample of LiH in stainless steel heating tube, and stainless steel heating tube is installed in reaction unit, after gas circuit being vacuumized and gets rid of air residual in gas circuit, the temperature controller parameter to 100 DEG C of setting reaction.
To be heated to design temperature 100 DEG C, be filled with rapidly 0.5 MPa ammonia, react 1 hour, stop testing, and the gas immediately in blowdown piping, treat that stainless steel heating tube is cooled to room temperature, take out reacted samples weighing and record dehydrogenation reaction productive rate.
Six, test result analysis:
Fig. 1 is Different L iNH 2the XRD comparison diagram of doping LiH sample after ball-milling processing, by contrasting the XRD standard card of several material, finds along with LiNH 2add the increase of per-cent, the LiNH in doped samples 2characteristic peak more and more obvious.Meanwhile, use Debye-Scherrer formula analysis through the LiNH of ball milling pretreatment 2particle size can reach Nano grade, can better be dispersed in LiH sample.
Fig. 2 adopts the inventive method under 100 DEG C of temperature of reaction conditions, four kinds of Different L iNH 2doping LiH sample and plain LiH respectively with the ammonia gas react productive rate comparison diagram of 1 hour.Find LiNH 2interpolation can improve dehydrogenation reaction productive rate, wherein along with the increase reaction yield of addition has the trend first increasing and reduce afterwards, work as LiNH 2liH sample when doping reaches 1 mol% is for best.
Fig. 3 is that LiNH is worked as in research separately 2liH sample when doping reaches 1 mol% and LiH sample respectively with the productive rate comparison diagram of ammonia gas react.Both discoveries reaction yield all increases along with the growth of temperature and time.But both, from time and temperature angle changing rate, work as LiNH 2doping be the LiH sample of 1 mol% and ammonia gas react productive rate at any temperature and time point all higher than plain LiH – NH 3system.LiNH is described 2the seed effect that LiH sample when doping reaches 1 mol% produces after reaction significantly can improve LiH – NH 3system dehydrogenation reaction kinetics.
Fig. 4 is doping 1 mol% LiNH 2liH sample and ammonia at 75 DEG C and 100 DEG C, under temperature of reaction condition, carry out the productive rate comparison diagram that reacts respectively, can find out that, in the same reaction time, the reaction yield at 100 DEG C is all better than 75 DEG C.
Fig. 5 is doping 1 mol% LiNH 2liH sample and the average yield comparison diagram of ammonia under 100 DEG C of differential responses time, by the average yield under map analysis different time points, find that the prolongation average response productive rate along with the time reduces gradually, illustrate that in 1 hour, speed of reaction is very fast.

Claims (6)

1. one kind is improved the dynamic (dynamical) LiH-NH of hydrogen storage system dehydrogenation 3method, is characterized in that comprising the following steps:
1) under an atmosphere of hydrogen, carrying out ball-milling processing by mixing with LiH after pre-for alkali metal amino compound ball milling, obtaining the LiH material of alkali doped amides;
2) in the absence of oxygen, expected by the LiH of alkali doped amides to carry out hydrogen discharge reaction with ammonia, reaction terminates rear cooling, obtains and improves the dynamic (dynamical) LiH-NH of hydrogen storage system dehydrogenation 3.
2. method according to claim 1, is characterized in that described alkali metal amino compound is LiNH 2.
3. method according to claim 2, is characterized in that LiNH described in the LiH material of alkali doped amides 2doping be 0.5 ~ 3mol%.
4. method according to claim 3, is characterized in that LiNH described in the LiH material of alkali doped amides 2doping be 1mol%.
5. method according to claim 1, is characterized in that described step 2) in, alkali doped amides is first placed in stainless steel tube, after emptying described stainless steel inner air tube, then passes into 0.5 MPa ammonia and carry out hydrogen discharge reaction.
6. method according to claim 1 or 5, is characterized in that described step 2) in, the temperature condition of described hydrogen discharge reaction is 100 DEG C, and the reaction times is 1 hour.
CN201510339530.3A 2015-06-18 2015-06-18 Preparing method for improving LiH-NH<3> hydrogen storing system dehydrogenizing kinetics Pending CN104925751A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106145031A (en) * 2016-07-06 2016-11-23 扬州大学 A kind of LiNH improving hydrogen storage property2the preparation method of LiH hydrogen storage material
CN112110426A (en) * 2020-08-20 2020-12-22 浙江工业大学 Method for synthesizing amino lithium potassium by mechanical ball milling
CN112110427A (en) * 2020-08-20 2020-12-22 浙江工业大学 Synthesis method of lithium potassium amino fluoride
CN117772259A (en) * 2024-02-26 2024-03-29 山东海化集团有限公司 Double-active-center ammonia synthesis catalyst and preparation method and application thereof

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CN102442646A (en) * 2010-10-13 2012-05-09 中国科学院大连化学物理研究所 High-capacity composite hydrogen storage material and hydrogen discharge method
CN103588171A (en) * 2013-10-24 2014-02-19 上海大学 Method of realizing circulating and quickly releasing hydrogen under microwaves of Li-N-H system

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106145031A (en) * 2016-07-06 2016-11-23 扬州大学 A kind of LiNH improving hydrogen storage property2the preparation method of LiH hydrogen storage material
CN112110426A (en) * 2020-08-20 2020-12-22 浙江工业大学 Method for synthesizing amino lithium potassium by mechanical ball milling
CN112110427A (en) * 2020-08-20 2020-12-22 浙江工业大学 Synthesis method of lithium potassium amino fluoride
CN117772259A (en) * 2024-02-26 2024-03-29 山东海化集团有限公司 Double-active-center ammonia synthesis catalyst and preparation method and application thereof

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Application publication date: 20150923