CN101696020B - Method for preparing efficient low-temperature ammonia-storing material - Google Patents
Method for preparing efficient low-temperature ammonia-storing material Download PDFInfo
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- CN101696020B CN101696020B CN2009101978608A CN200910197860A CN101696020B CN 101696020 B CN101696020 B CN 101696020B CN 2009101978608 A CN2009101978608 A CN 2009101978608A CN 200910197860 A CN200910197860 A CN 200910197860A CN 101696020 B CN101696020 B CN 101696020B
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- ammonia
- amino borane
- temperature
- borane
- amino
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Abstract
The invention belongs to the technical field of compound preparation and gas storage, and specifically relates to a method for preparing efficient low-temperature ammonia-storing material. The method comprises: placing amino borane in a sealed container; performing vacuumization; allowing the amino borane to be in contact with ammonia at a temperature between 0 and 4 DEG C; keeping the two at a temperature between 0 and 4 DEG C for 30 to 60 minutes; and obtaining a needed product. The ammonia content of the product is regulated according to different ammonia pressures, and the relationship between the ammonia content and the ammonia pressure at 0 DEG C is: n = 0.1 X3-0.7 X2 + 2.1 X - 0.2, wherein X is the ammonia pressure; bar is a unit; and n is the number of ammonia absorbed by each mol of amino borane. Amino borane ammonia complex NH3BH3(NH3)n(n=1-3) is obtained through preparation. The amino borane is completely reversible in absorbing and releasing ammonia, and when the amino borane is used to store ammonia gas, the maximum amount of stored ammonia can be up to 62.4 percent by weight, and room-temperature gas supply pressure is about 2.0 bar. The amino borane has the advantages of large ammonia-storage amount (the highest ammonia-storage amount of the amino borane can be up to 76.7 percent by weight), moderate room-temperature gas supply pressure and completely reversible capability of absorbing and releasing ammonia.
Description
Technical field
The invention belongs to compound and atmosphere storage technical field, be specifically related to a kind of preparation method of efficient low-temperature ammonia-storing material.
Background technology
Ammonia is as a kind of important chemical feedstocks, and is industrial in modern times, agricultural, and environment protection, many aspects such as scientific research have a wide range of applications.Like automobile, the NO in the waste gas of boiler and process furnace
xBring serious light pollution and toxicity, seriously influenced the Human's production life, used ammine selectivity catalytic reduction (Selective Catalytic Reduction, SCR) NO
xCan effectively reduce its discarded pollution, this technology is commercial applications in developed country coal-burning power plants such as Europe, U.S.A, day.
[1]Its catalyzed reaction principle mainly comprises:
[2-6]
4NH
3+4NO+O
2→4N
2+6H
2O；4NH
3+6NO→5N
2+6H
2O；
8NH
3+6NO
2→7N
2+12H
2O；4NH
3+2NO
2+2NO→4N
2+6H
2O
Be not difficult to find out that from above-mentioned principle reaching of best catalytic conversion must be controlled NH accurately
3IR, guarantee that above-mentioned chemistry side should carry out with stoichiometric ratio, avoids NH
3Excessive and insufficient situation.
In the use of ammonia, the storage of ammonia is an important step, and ammonia storage means commonly used has the steel cylinder storage, and is water-soluble, or solid absorption.For gaseous ammonia or ammoniacal liquor, because ammonia has stronger corrodibility, transportation high pressure ammonia is abnormally dangerous, and container possibly explosion cause deleterious emission intensity, has limited its application.Recently the researchist proposes to utilize metal-salt as storage and the solid material of carrying ammonia.Because the alkaline earth metal ion salt can well be inhaled and put ammonia, so its ammonia complex provides a kind of safety, lightweight, cheap and fine and close file layout.But to be the system operation temperature higher (for example discharges MgCl for its tangible deficiency
2(NH
3)
6In all ammonia to be higher than 450 ℃), ammonia release temperature span is big (100 ℃-600 ℃), limited its application to a certain extent.
[7.8]
Adopt the ammonia complex of amino borane of the present invention can overcome above-mentioned part shortcoming.Experiment confirm, amino borane be below 10 ℃, and storage that can completely reversibility is greater than the ammonia of 60wt.%.Experimental observation becomes liquid after amino borane is inhaled ammonia fully.Compare with existing ammonia-storing material, ammonia release temperature of the present invention is moderate, and ammonia is pressed lower; Storage ammonia amount is big, light practicality.
Reference:
[1]Soud?H?N，Fukasawa?K.Developments?in?NO
x?abatement?and?control.London：IEA?CoalRe2，search，1996，62-68。
[2]Chemical?and?Engineering?News，14?April，1997，p.12。
[3]Ronald?M.Heck，Catal.Today，1997，53，519-523。
[4]Howard?L.Fang，Herbert?F.M.DaCosta，Appl.Catal.B：Environmental，2003，46，17。
[5]Chemical?Engineering?Progress，January?1994，p.39。
[6]Koebel?M，Madiag，Elsener?M.，Catal.Today，2002，73，239-247。
[7]Liu?Chun?Yi，AiKa，Bull.Chem.Soc.Jpn.2004，77，123-131。
[8] C.H. Harald Christensen, T. John Nei Sen, U. overstates moral, J.K. Nei Sike, the R.Z. Ange SOrensen, invention special column title:
The solid material of storage and conveying ammonia, 200580026626.9.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of efficient low-temperature ammonia-storing material.
The efficient low-temperature ammonia-storing material that the present invention proposes, its structural formula is: NH
3BH
3(NH
3)
n, wherein n is 1-3.
The preparation method of the efficient low-temperature ammonia-storing material that the present invention proposes, concrete steps are following: amino borane is placed encloses container, vacuumize, under 0-4 ℃ of temperature, contact with ammonia, under 0-4 ℃ of temperature, kept 30-60 minute, prepare required product; The difference of pressing according to ammonia can be regulated the ammonia quantity of product, and the relation of ammonia quantity and ammonia pressure is in the time of 0 ℃: n=0.1X
3-0.7X
2+ 2.1X-0.2., wherein X is that ammonia is pressed, and unit is bar, and n is that every mole of amino borane is inhaled the ammonia number.
Among the present invention, said ammonia source is ammonia or liquefied ammonia.Ammonia pressure (or dividing potential drop) in the time of should inhaling the selected preparation of ammonia number according to target in the specimen preparation process.
Among the present invention, use amino borane and carry out the ammonia storage, use temperature should not be higher than 80 ℃, and maximum storage ammonia amount 62.4wt.% is about room temperature supply gas pressure 2.0bar.
Beneficial effect of the present invention is: amino borane storage ammonia amount big (the highest storage ammonia of amino borane amount can reach 76.7wt.%), room temperature supply ammonia pressure moderate, inhale and put the ammonia completely reversibility.
Description of drawings
Fig. 1 depresses the suction ammonia of amino borane and discharges ammonia TPD curve for 1.2bar ammonia.
Fig. 2 depresses the suction ammonia of amino borane and discharges ammonia TPD curve for 1.4bar ammonia.
Fig. 3 depresses the suction ammonia of amino borane and discharges ammonia TPD curve for 1.6bar ammonia.
Fig. 4 depresses the suction ammonia of amino borane and discharges ammonia TPD curve for 1.8bar ammonia.
Fig. 5 depresses for 2.5bar ammonia, and 0 ℃ of amino borane is inhaled ammonia TPD curve.
Fig. 6 is put the XRD comparison diagram of ammonia gained amino borane for the amino borane raw material and after 3bar ammonia is depressed suction ammonia.
Fig. 7 inhales the ammonia amount for the difference that the different ammonia of amino borane are depressed.
Embodiment
Further specify the present invention through embodiment below.
Embodiment 1:NH
3BH
3(NH
3)
1.3Preparation discharges instance with ammonia:
Get amino borane (＞97%) 0.150g and place the closed stainless steel container, stainless steel vessel is vacuumized, place mixture of ice and water (0 ℃-4 ℃), pour the 1.2bar ammonia fast, static 40 minutes, make NH
3BH
3(NH
3)
1.3With 1 ℃/min heating mixture of ice and water, discharge ammonia at the 1.2bar ammonia.Test result is as shown in Figure 1.As we can see from the figure, amino borane was inhaled the ammonia rapid speed at preceding 15 minutes, through about 40 minutes, basically no longer inhaled ammonia, and every mole of amino borane of result of calculation is drawn 1.3 ammonia.It is put the ammonia curve and shows that amino this that preceding step amino borane is drawn is all emitted.
Embodiment 2:NH
3BH
3(NH
3)
3Preparation:
Get amino borane (＞97%) 0.150g and place the closed stainless steel container, stainless steel vessel is vacuumized, place mixture of ice and water (0 ℃-4 ℃), pour the 2.5bar ammonia fast, static more than 40 minutes, promptly get NH
3BH
3(NH
3)
3Test result corresponding diagram 5.Can see that from figure inhale ammonia with respect to the amino borane that 1.2bar ammonia is depressed, the suction ammonia speed that 2.5bar ammonia is depressed is obviously accelerated.Fig. 6 be suction put before and after the ammonia XRD relatively, can be converted into amino borane fully after can seeing amino borane amide deamination, prove that the ammonia characteristic is put in the reversible suction of this system.
Claims (3)
1. the preparation method of an efficient low-temperature ammonia-storing material is characterized in that concrete steps are following: amino borane is placed encloses container, vacuumize, under 0-4 ℃ of temperature, contact with ammonia, under 0-4 ℃ of temperature, kept 30-60 minute, prepare required product; The ammonia quantity of the different adjustment product of pressing according to ammonia, the relation of ammonia quantity and ammonia pressure is in the time of 0 ℃: n=0.1X
3-0.7X
2+ 2.1X-0.2, wherein X is that ammonia is pressed, and unit is bar, and n is that every mole of amino borane is inhaled the ammonia number.
2. the preparation method of efficient low-temperature ammonia-storing material according to claim 1 is characterized in that said ammonia is ammonia or liquefied ammonia.
3. the ammonia-storing material that obtains of preparation method according to claim 1 is characterized in that its structural formula is: NH
3BH
3(NH
3)
n, wherein n is 1-3.
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| CN101696020A CN101696020A (en) | 2010-04-21 |
| CN101696020B true CN101696020B (en) | 2012-01-18 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2388058A1 (en) * | 2010-05-19 | 2011-11-23 | Amminex A/S | Method and device for re-saturation of ammonia storage material in containers |
| CN102030313B (en) * | 2010-11-26 | 2012-07-04 | 南开大学 | Organic matter and ammonia borane compounded hydrogen storage material and preparation method thereof |
| CN103569967B (en) * | 2013-11-18 | 2015-10-28 | 复旦大学 | A kind of preparation method of ammonia borine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108737A (en) * | 2007-04-26 | 2008-01-23 | 浙江理工大学 | Use of by-product of silicone hydride produced by magnesium silicide method |
| CN101182006A (en) * | 2007-11-15 | 2008-05-21 | 浙江大学 | Amido complex compound and preparation method and usage |
-
2009
- 2009-10-29 CN CN2009101978608A patent/CN101696020B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108737A (en) * | 2007-04-26 | 2008-01-23 | 浙江理工大学 | Use of by-product of silicone hydride produced by magnesium silicide method |
| CN101182006A (en) * | 2007-11-15 | 2008-05-21 | 浙江大学 | Amido complex compound and preparation method and usage |
Non-Patent Citations (2)
| Title |
|---|
| Jinshan Li et al..B-Hδ- σ bond as dihydrogen bond acceptor: some theoretical observations and predictions.《Journal of chemical physics》.2002,第116卷(第1期),第25-32页. * |
| Yun Meng et al..Non-conventional hydrogen bonding interaction of BH3NH3 complexes: a comparative theoretical study.《THEO CHEM》.2005,第713卷第135-144页. * |
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