CN103832983A - Synthesis method of amino metal compounds - Google Patents
Synthesis method of amino metal compounds Download PDFInfo
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- CN103832983A CN103832983A CN201210487046.1A CN201210487046A CN103832983A CN 103832983 A CN103832983 A CN 103832983A CN 201210487046 A CN201210487046 A CN 201210487046A CN 103832983 A CN103832983 A CN 103832983A
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Abstract
The invention discloses a synthesis method of amino metal compounds. Series of metal unitary or binary amino compounds are successfully synthesized by using a mechanical ball milling method in a ball-milling atmosphere controlled manner through combination of a subsequent method of roasting crystallization controlled under a low-pressure atmosphere. Compared with the traditional high-temperature and high-pressure roasting method, the synthesis method disclosed by the invention is simple and safe to operate, high in yield and low in cost, thereby providing the foundation for the compounds applied to hydrogen storage systems.
Description
Technical field
The present invention relates to the technology of preparing of metal amino compound, specifically for synthetic metal amino compound provides a kind of simple to operate, safe and reliable, preparation method that cost is low.
Background technology
In recent years, worldwide energy dilemma and environmental degradation impel people to set up new forms of energy system more efficient, recyclable regenerative.Hydrogen is because its reserves are abundant, and combustion heat value is high and pollution-free and become the important composition of future source of energy system.Need mainly solve the preparation of hydrogen to the utilization of Hydrogen Energy, store, several gordian techniquies such as transportation, this wherein hydrogen storage technology be comparatively weakness link.Especially at present automotive industry faces transition, at its automobile that taps a new source of energy, as hydrogen fuel cell automobile, in the processes such as hydrogen internal combustion engine automobile, onboard hydrogen source problem and hydrogen storage system exploitation are to be badly in need of one of Pinch technology overcoming, and Ge great motor corporation and national scientific research institution all drop into exploitation and the research of huge fund for novel hydrogen storage material.Alkalies and alkaline earth aminocompound (amide)-hydride (hydride) system is the efficient hydrogen storage material of a class of recently researching and developing.Compared to traditional transition metal alloy compound, this material system has higher storage Hydrogen Energy metric density, can partly meet the vehicle-mounted hydrogen storage system technical requirements that american energy office formulates.As amino magnesium-lithium hydride (Mg (NH
2)
2-LiH) system can be under 180 degrees Celsius reversible suction hydrogen 5.5% weight ratio.Sandia National Laboratory of the U.S., by test, confirms that its cycle life is more than 200 times.Thermodynamics calculates that desorption temperature corresponding to this hydrogen storage system one normal atmosphere equilibrium pressure can be low to moderate 90 degrees Celsius, reached the operating temperature range of Proton Exchange Membrane Fuel Cells.Experimentally, by adding potassium catalyzer, greatly reduced Mg (NH
2)
2-LiH system dehydrogenation kinetics resistance, desorption temperature is inhaled in circulation can be reduced to 107 degrees Celsius, extremely approaches theoretical value.This system has become the U.S. at present, the complex of the practical hydrogen storage technology of Japan's exploitation, and domestic in the 973 storage hydrogen projects of grinding, this system has also been used to amplify, and practical test is reached in tinning.For the fast-developing and follow-up possible application of amide-hydride hydrogen storage system, just become very important as preparation technology's exploitation of the alkalies and alkaline earth aminocompound of one of raw material.With respect to all kinds of hydride that can extensively buy, the aminocompound product of business is very limited at present, only has Lithamide (LiNH
2) and sodium amide (NaNH
2), and expensive, the totally unfavorable application on hydrogen storage technology in amide-hydride system.Traditional metal amino compounds process for production thereof mainly adopts direct ammonification metallic particles technology, annotate liquefied ammonia to being equipped with in the autoclave of metallic particles, synthetic under high temperature (>300 degree Celsius), high pressure (>1Gpa).The difficult point of the method is that adopted liquefied ammonia at high temperature can produce extremely high pressure, and this security to reactor has high requirement.Because general preparation process all adopts reactor pressure-bearing, it is excessive that kettle internal volume is difficult for design, thereby cause batch output impossible high.In addition, owing to pressing and promote reaction by high ammonia, ammonia is seriously excessive, makes also to need after end of synthesis to reclaim residue liquefied ammonia, comparatively complicated in operation.Thereby a kind of cheapness of urgent need exploitation, easy-operating, safe and reliable preparation technology is for the production of aminocompound.
Summary of the invention
The present invention makes every effort to provide a kind of simple to operate, safe, metal amino compounds process for production thereof cheaply.Particular content is, adopts self-control ball grinder to implement ball milling under ammonia closed atmosphere, and in mechanical milling process, along with the reducing of metal or metal hydride size, it reacts rapidly with ammonia, thereby avoids raw material adhesion.Owing to having reduced particle size and reaction kinetics resistance, ball milling method can guarantee thermodynamics allow reaction process carry out completely, the thermopositive reaction between this very applicable ammonia and metal and metal hydride.Thus, by controlling ammonia total amount in tank body, reach its with metal or metal hydride between stoichiometric reaction, realized and in mechanical milling process, directly synthesized target aminocompound.Because ball milling product is generally amorphous, can be by the powder making in the roasting of ammonia atmosphere mesolow, thus obtain the metal amino compound of crystallization.
Aforesaid metal amino compound chemistry general formula is M
x(NH
2)
y, in formula, M is all alkali and alkaline earth metal ions of the periodic table of elements, and a kind of or wherein combination of any two kinds of elements of the main group triels such as Al, wherein 0<x≤4,0<y≤20.
Aforesaid special ball grinder is stainless cylinder of steel sealable, pressure-bearing, is equipped with and the valve being communicated with in tank, for pass into gas purging in gas and tank in tank on cover.
The specific operation process that the present invention prepares metal amino compound is: in argon gas glove box, accurately take metal or metal hydride raw material, be encased in special ball grinder and complete tank body sealing.After ball grinder is shifted out to glove box, outside glove box, according to stoichiometric, the valve by ball grinder caping injects quantitative ammonia to one or many in ball grinder.Conventionally the mol ratio of ammonia and metal or metal hydride is 0.1～20.After planetary ball mill, start ball milling at installation tank body, machine rotational speed is set as 50～400rpm, and material ball ratio is 0.1～100.In mechanical milling process, determine reacting finisheding degree by ammonia residual content in real-time detection tank.Concrete detection method can adopt gaseous mass analyzer, or adopts easy cobalt nitrate aqueous solution method of inspection, passes in the reagent bottle that cobalt nitrate aqueous solution is housed by the gas in ball grinder.If it is blue that red cobalt nitrate aqueous solution can become, illustrate that in tank, ammonia unreacted is complete, need to extend the ball-milling reaction time; If red cobalt nitrate aqueous solution nondiscoloration, illustrates that reaction is complete, now stop ball milling, in argon gas glove box, sample is taken out.For obtaining crystalline products, milled sample can be carried out to roasting, roasting is to carry out under 0.5～10atm ammonia is calmed the anger atmosphere, and maturing temperature is 100～500 ℃, and roasting time is 0.5～150h.
The present invention has the following advantages:
1. adopt solid phase mechanical ball milling, can reduce particle size to hundred nano-scale, thereby greatly improve solid state reaction interface, shorten diffusion length, augmenting response performance.By using mechanical ball milling can reduce metal particle size, improve its reactivity, thereby can weaken the demand to high pressure ammonia, improve synthetic security.
2. metal is generally ductile, and is easy to be attached to ball milling tank base under ball action, thereby greatly reduces grinding efficiency, is difficult to obtain nanometer grade gold metal particles, especially for soft alkalies and alkaline earth under general ball milling condition.But the present invention adopts self-control ball grinder, realize ball milling under ammonia closed atmosphere, allow metallic particles react rapidly with ammonia in size reduction, avoid metal adhesion, realize and in mechanical milling process, directly synthesize required metal amino compound.
3. storage hydrogen research does not need the aminocompound of crystallization, follow-uply unbodied ball milling material directly can be added in ball grinder and mixes with hydride, makes amide-hydride mixture for storing up hydrogen research.But as sintetics, the metal amino compound of crystallization can adopt roasting method to obtain, and now no longer needs high ammonia to press, under normal pressure ammonia atmosphere, roasting can make, thus the security that has greatly improved preparation process.
Preparation method's technique of the metal amino compound that the present invention proposes is simple, safe and reliable, can greatly reduce costs.At present existing technical grade ball milling tank body can be amplified to a cube meter level, and this makes to utilize the inventive method can in the short period of time, obtain the throughput of hundred feather weight metal amino compound even tonne.
Accompanying drawing explanation
Fig. 1. the X-ray powder diffraction figure of amino magnesium;
Fig. 2. the X-ray powder diffraction figure of amino calcium;
Fig. 3. the X-ray powder diffraction figure of Lithamide aluminium.
Specific embodiment
The present invention adopts mechanical ball milling method to realize ammonia and metal or metal hydride single step reaction, prepares metal amino compound.By the following examples the present invention is described in detail, it is to be noted that the present invention is not limited to these embodiment.
Embodiment 1:
Amino magnesium is preparation Mg (NH
2)
2the important source material of-LiH high-performance hydrogen storage material, but this raw material there is no commerical prod.The present invention adopts 200 milliliters of stainless steel jar mill, and 15 millimeters of Stainless Steel Balls of built-in diameter, are equipped with gas switch valve on cover, can pass into quantitative gas sealing in the inner.In argon gas glove box, accurately take 12 grams of (0.5 mole) particle diameters in the magnesium granules of 2 millimeter or length at the magnesium sheet (the pellet mass ratio of ball milling is 1:100) of 5 millimeter, be placed in ball grinder and sealing.Cover valve by ball grinder afterwards and pass into 8.5 grams of (0.5 mole) pure ammonias in tank, tank internal pressure is about 8atm(ammonia and liquefies in tank).After valve-off, ball grinder is placed in to planetary ball mill (Retsch, PM400) upper, it is 200 revs/min of rotating speeds that ball milling condition is set, and every ball milling shuts down 20 seconds for 5 minutes, then reverse rotation 5 minutes, reaches and so forth total Ball-milling Time 2 hours.Take off afterwards ball grinder, the hydrogen generating in tank and the unreacted ammonia of part are discharged, add again 8.5 grams of pure ammonias, repeat above-mentioned mechanical milling process simultaneously.Ball milling intermittence and the time of termination, adopt Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (Co (NO
3)
2) whether solution absorption process simple test gaseous product remain ammonia.As without ammonia being detected, prove that gas-solid reaction finishes.Follow-uply confirm that by samples weighing all magnesium is converted into amino magnesium, actual measurement rate of body weight gain is 133%, consistent with theoretical value.As still have ammonia to exist and cause Co (NO
3)
2solution colour, by red stain indigo plant, extends Ball-milling Time until ammonia approach exhaustion.Now, as need are prepared Mg (NH
2)
2-LiH hydrogen storage material, can directly add lithium hydride powder by stoichiometric ratio and implement ball milling.In this experiment, the amino magnesium output of single tank is 28 grams, reaches more than 95% through thermogravimetric and X light powder diffraction analysed preparation purity.Concrete amino magnesium preparation feedback equation is,
Mg+2NH
3→Mg(NH
2)
2+H
2
The amino magnesium that above-mentioned ball milling makes is amorphous, follow-uply by its crystallization process is: the amino magnesium that ball milling is made is placed in a horizontal tubular reactor, and pressed powder is dispersed, without compressing tablet.Be warming up to 320 ℃ importing after a small amount of ammonia is pressurized to 2atm in by pipe, and keep 24 hours.The white powder solid finally making turns out to be the amino magnesium of crystallization through X light diffracting analysis, purity remains on more than 95%.
Embodiment 2:
Consider the economic and practical of hydrogen storage material, metal in Amide-hydride system preferably adopts cheap alkaline-earth metal, recently the research that contains amino calcium hydrogen storage system is progressively increased, thereby cause amino calcium demand to increase, but this compound does not exist equally without commerical prod.Adopt the synthetic method of similar amino magnesium can realize the amino calcium of preparation.Concrete grammar is: in argon gas glove box, accurately take 20 grams of reguline metal calcium (the pellet mass ratio of ball milling is 1:150), and be placed in ball grinder.Because the calcium metal that used is here large bulk, can before ball milling, pass into a small amount of ammonia (approximately 2 grams) adsorption in calcium piece, utilize infiltration, the diffusion of gas and act on and reach preliminary efflorescence effect with it, this can improve follow-up grinding efficiency greatly.Be down to (ammonia now is not converted to hydrogen, but many adsorptions are in metallic surface) after negative pressure in tank internal pressure, continue to add 6.5 grams of ammonias.Now ball grinder is placed on ball mill and starts ball-milling processing, speed setting is 200 revs/min, every ball milling 5 minutes 20 seconds out of service, after reverse rotation 5 minutes again, within 20 minutes, complete and so forth reaction process.Discharge the hydrogen generating, add 8.5 grams of ammonias to continue ball milling 20 minutes simultaneously, record ammonia and all consume.The follow-up sample of weighing finds that weightening finish exceedes 80%, and this conforms to theoretical weightening finish.More what is interesting is, because pass into a small amount of ammonia carry out pre-reaction early stage, efflorescence bulk metal, has avoided subsequent ball milling overlong time and causes material decrystallized.The pressed powder that this building-up process obtains directly presents splendid amino calcium diffraction spectrogram, thereby has directly saved follow-up roasting crystallization process.Obtain this product purity more than 97% from X light powder diffraction atlas analysis.The reaction formula that concrete preparation process relates to is as follows:
Ca+2NH
3→Ca(NH
2)
2+H
2
Embodiment 3:
The optimization of Amide-hydride hydrogen storage system is be unable to do without the modulation of metallic cation wherein, because this can realize the strong modulation of metal-nitrogen key key, many metal components should be one of developing direction of following Amide-hydride system, are necessary to realize the synthetic amplification of multi-element metal aminocompound for this reason.Binary LiAl (NH
2)
4the synthetic pre-burned LiAl alloy that adopts of tradition, follow-up itself and liquefied ammonia heated and realized under High Temperature High Pressure.The method energy consumption is large, and safety coefficient is low, and alloying requires high.The present invention directly adopts LiAlH
4complex hydride ammonating process, similar amino calcium synthesis technique, synthesizes the LiAl (NH of high-quality
2)
4aminocompound.Concrete grammar is: in argon gas glove box, accurately take powdery LiAlH
4solid 19 grams (0.5 moles) is placed in ball grinder (the pellet mass ratio of ball milling is 1:150), the rear ammonia that slowly passes into, and because this gas-solid reaction is exothermic process, and thermal discharge is larger, therefore ammonia adds more aforementioned two building-up processes more slow.Adding valve-off after quantitative ammonia, starting 120 revs/min of lower milled samples 10 minutes.Discharge the hydrogen generating when constant and again slowly add ammonia to continue ball milling monitoring tank internal pressure, so replacing ball milling and generate to not detecting hydrogen for several times, showing that aminating reaction finishes.It is 157% that weighing obtains sample weightening finish, approaches theoretical value.X light powder diffraction confirms approximately 50 grams of LiAl (NH that solid product is crystallization of gained simultaneously
2)
4, analyze its purity more than 97%.Specifically aminating reaction process is,
LiAlH
4+4NH
3→LiAl(NH
2)
4+4H
2。
Claims (6)
1. a synthetic method for metal amino compound, is characterized in that: preparation process mainly comprises batching, ammonification, ball milling, roasting;
Take metal or metal hydride and ammonia as raw material, adopt ball milling method, press by controlling ammonia in ball grinder, realize ammonia and measure and react with metal or Metal hydride chemistry; The mol ratio of ammonia and metal or metal hydride is: 0.1～20;
Carry out ball milling: ball milling adopts planetary ball mill, and rotational speed of ball-mill is 50～400rpm, and the pellet mass ratio of ball milling is: 0.005～10;
The product taking out after ball milling carries out roasting, and roasting condition is to be 0.5～10atm in ammonia pressure, and maturing temperature is 100～500 ℃, and roasting time is 0.5～150h.
2. preparation method as claimed in claim 1, is characterized in that: described metal is the combination of one or two or more kinds element in basic metal, alkaline-earth metal and the 3rd main group element, and the chemical general formula of corresponding aminocompound is M
x(NH
2)
y, 0<x≤4 in formula, 0<y≤20.
3. preparation method as claimed in claim 1, is characterized in that: described ball grinder is sealable, high voltage bearing ball grinder, is equipped with and the valve being communicated with in tank, for passing into or Exhaust Gas in tank on cover.
4. preparation method as claimed in claim 1, it is characterized in that: described ammonification, according to the stoichiometric of ammonia and raw material, the valve covering by ball grinder passes into quantitative ammonia above to disposable in ball grinder or a point secondary, and the mol ratio of ammonia and metal or metal hydride is: 0.1～20.
5. preparation method as claimed in claim 2, it is characterized in that: described metal hydride is the combination of one or two or more kinds element in alkalimetal hydride, alkaline earth metal hydride and the 3rd main group element hydride, the chemical general formula of corresponding aminocompound is M
x(NH
2)
y, 0<x≤4 in formula, 0<y≤20.
6. the preparation method as described in claim 2 or 5, is characterized in that:
Described the 3rd main group element is Al or Ti.
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Cited By (9)
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| CN105776132A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院大连化学物理研究所 | Method for cheaply and extensively preparing nitrogen-based metal compound hydrogen storage material |
| CN106881132A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing ammonia |
| CN110938431A (en) * | 2019-11-13 | 2020-03-31 | 西南林业大学 | Preparation method of bio-based natural fluorescent whitening agent |
| CN112062110A (en) * | 2020-08-14 | 2020-12-11 | 浙江工业大学 | Method for synthesizing binary metal amino compound |
| CN112079331A (en) * | 2020-08-20 | 2020-12-15 | 浙江工业大学 | Synthesis method of metal-nitrogen-hydrogen system hydrogen storage material |
| CN112110425A (en) * | 2020-08-14 | 2020-12-22 | 浙江工业大学 | Synthesis method of amino lithium potassium |
| CN112142024A (en) * | 2020-08-14 | 2020-12-29 | 浙江工业大学 | Synthesis method of alkali metal amino compound |
| CN112265958A (en) * | 2020-10-29 | 2021-01-26 | 中国计量大学 | Composite hydrogen storage material and preparation method thereof |
| CN112981155A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method of binary intermetallic compound |
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Cited By (12)
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| CN105776132A (en) * | 2014-12-16 | 2016-07-20 | 中国科学院大连化学物理研究所 | Method for cheaply and extensively preparing nitrogen-based metal compound hydrogen storage material |
| CN105776132B (en) * | 2014-12-16 | 2019-04-23 | 中国科学院大连化学物理研究所 | A kind of method of cheap large scale preparation nitrogen metal carbonyl compound hydrogen storage material |
| CN106881132A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing ammonia |
| CN106881132B (en) * | 2015-12-15 | 2020-04-24 | 中国科学院大连化学物理研究所 | Catalyst for synthesizing ammonia |
| CN110938431A (en) * | 2019-11-13 | 2020-03-31 | 西南林业大学 | Preparation method of bio-based natural fluorescent whitening agent |
| CN112981155A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Preparation method of binary intermetallic compound |
| CN112062110A (en) * | 2020-08-14 | 2020-12-11 | 浙江工业大学 | Method for synthesizing binary metal amino compound |
| CN112110425A (en) * | 2020-08-14 | 2020-12-22 | 浙江工业大学 | Synthesis method of amino lithium potassium |
| CN112142024A (en) * | 2020-08-14 | 2020-12-29 | 浙江工业大学 | Synthesis method of alkali metal amino compound |
| CN112079331A (en) * | 2020-08-20 | 2020-12-15 | 浙江工业大学 | Synthesis method of metal-nitrogen-hydrogen system hydrogen storage material |
| CN112265958A (en) * | 2020-10-29 | 2021-01-26 | 中国计量大学 | Composite hydrogen storage material and preparation method thereof |
| CN112265958B (en) * | 2020-10-29 | 2022-06-24 | 中国计量大学 | Composite hydrogen storage material and preparation method thereof |
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Application publication date: 20140604 |