CN102225747B - Synthesis method of calcium borohydride by normal-temperature solid-phase ball milling - Google Patents
Synthesis method of calcium borohydride by normal-temperature solid-phase ball milling Download PDFInfo
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- CN102225747B CN102225747B CN 201110145490 CN201110145490A CN102225747B CN 102225747 B CN102225747 B CN 102225747B CN 201110145490 CN201110145490 CN 201110145490 CN 201110145490 A CN201110145490 A CN 201110145490A CN 102225747 B CN102225747 B CN 102225747B
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Abstract
This invention relates to preparation of inorganic and solid materials, and specifically relates to a synthesis method of calcium borohydride by solid-phase ball milling of reactants at a certain hydrogen pressure. The synthesis method of calcium borohydride by normal-temperature solid-phase ball milling is performed by reacting on calcium hydride and calcium boride used as the reaction starting materials by using transition metal elements as the catalyst under the action of mechanical force at a hydrogen pressure of 10-150 atm at normal temperature. The synthesis method provided by the invention has the advantages of simple process and equipment, adjustable and controllable reaction process, mild reaction conditions, high safety, etc.
Description
Technical field
The present invention relates to the preparation of inorganic and solid material, be specifically related to a kind of through to reactant in solid phase and apply under the condition of certain hydrogen pressure method through the synthetic hydroboration calcium of ball milling.
Background technology
Along with modern society's industriallization and modern high speed development, human demands for energy is grown with each passing day, requirement on environmental protection is improved day by day, this pollution to environment with the limited storage of existing fossil resource and its use generation has formed the contradiction of giving prominence to.Hydrogen Energy has and uses and development potentiality as the energy a kind of cleaning, wide material sources and that can be recycled.The key issue that the use of Hydrogen Energy need solve is its storing technology, and the storage method of hydrogen mainly contains solid-state storage hydrogen, liquid storage hydrogen and high-pressure gaseous storage hydrogen three major types at present.Solid-state hydrogen storage technology is than liquid, gaseous state high-pressure hydrogen storing technology, and it is good to have a security, and characteristics such as energy efficiency height are a kind of comparatively ideal hydrogen storage methods.In numerous solid-state hydrogen storage medias, the light-weight metal hydroborate is because its high hydrogen-storage amount, can satisfy Hydrogen Energy in practice to the requirement aspect energy efficiency, stability and the security, have development and application prospect.Wherein, hydroboration calcium has high quality hydrogen-storage amount (11.4 wt.%) and volume hydrogen-storage amount (~ 130 kg/m
3), be 32 kJ/mol H through the decomposition enthalpy that calculates gained
2, be in the desirable enthalpy scope of practice, received domestic and international investigator's extensive attention at present.In addition, hydroboration calcium is applied to the reduction of aldehyde, ketone, carboxylic acid and verivate thereof, acid amides, imines, nitrile, epoxy compounds, eneyne etc. at industrial circle.The low-cost industrialization preparation of hydroboration calcium is the basis of hydroboration calcium as the research and development of hydrogen storage material and other application.Owing to the synthetic difficulty of hydroboration calcium, cause its price extremely expensive, and mainly control at present by offshore company of several family.
Hydroboration calcium synthetic of report mainly contains two types of liquid phase method and solid phase methods in the world.
A kind of method of the synthetic hydroboration calcium of liquid phase method is to carry out through the ion exchange reaction between alkali metal borohydride and the calcium halide, and its related reaction equation is:
It is that reactant is adopted the organic solvent soaking extraction milled product again after solid phase is carried out ball milling, and the organic solvent that is adopted needs to dissolve institute's synthetic hydroboration calcium, but does not dissolve other reaction product and reaction residue.Milled product need stir in the Glass Containers of corresponding organic solvent is housed for a long time, with leaching hydroboration calcium wherein.Through filtering or centrifugal treating obtains the hydroboration calcium solution, obtain metal borohydride through processing such as desolvate again.Stir for a long time the stopping property of glass system is had relatively high expectations.In this liquid phase method, though this kind method cost is lower, by-products content is very high, and the purification difficult of sample only is applicable to breadboard a small amount of preparation, is not suitable for scale preparation.In addition, the long stirring had relatively high expectations to the stopping property of leaching container in the hydroboration calcium leaching process.
With hydrolith and the liquid wet chemical method that refluxes of triethylamine borine is the method for another kind of liquid phase production hydroboration calcium, and the equation of its reaction is:
This method relates to repeatedly washing and the drying of organic solvent to product, and process is loaded down with trivial details, and employed triethylamine borine is poisonous and cost an arm and a leg, and has not only increased production cost, and also there is threat in safety of operators.Thereby also there is suitable limitation in this method in practical application.
The method that adopts the synthetic hydroboration calcium of solid phase method mainly is that start material is mixed back thermal treatment to mixed reactant enforcement comparatively high temps under higher hydrogen pressure.The method of its reaction is generally:
An important condition of the synthetic hydroboration calcium of such solid state reaction is to adopt high temperature and high pressure; Its temperature of reaction is usually above 400 ℃; Required hydrogen pressure (needs 400 –, 700 normal atmosphere/bar) usually up to hundreds of normal atmosphere; Like the disclosed technical scheme of U.S. Pat 7608233B1, the time of reaction also reaches tens hours usually under HTHP, and the preparation process has certain danger.In reaction, also have report to adopt titanium trifluoride can lower temperature of reaction and reaction hydrogen pressure to a certain extent, but the decline degree is still very limited as catalyzer based on reaction (3).The harsh reaction conditions of HTHP and required special reaction device thereof have all improved the preparation cost of this method.
In sum, the preparation method of existing hydroboration calcium exists the preparation process complicated, severe reaction conditions, and security is low, and problems such as the purity of synthetic hydroboration calcium is lower, purification difficult, cost height can not satisfy the requirement that the mass-producing of hydroboration calcium is used.Therefore, it is significant to invent the compound method of the hydroboration calcium that a kind of preparation condition is gentle, technological process is simple and easy to control, safe and reliable, with low cost.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing technology of preparing, a kind of method of under gentle relatively condition, synthesizing hydroboration calcium is provided.
In order to realize above-mentioned purpose, the technical scheme below the present invention has adopted:
The method of the synthetic hydroboration calcium of a kind of normal temperature solid phase ball milling; This method is in 10～150 atmospheric hydrogen atmospheres at hydrogen pressure; Under the normal temperature condition with hydrolith and calcium boride as start material matter; Adopting transition metal is that catalyzer reacts under the effect of mechanicals efforts and makes, and its chemical equation is following:
Normal temperature of the present invention refers generally to such an extent that be 10～30 ℃ general temperature.
As preferably, above-mentioned transition metal is one or more among Fe, Co, Ni, Zr, Ti, V, Nb, Mo, Ru, Pd, Pt, Rh and the Hf.
As preferably, above-mentioned catalyzer is selected one or more in transition metal simple substance, transition metal halide and the transition metal oxide for use.
As most preferably, above-mentioned transition metal halide catalyst is FeCl
3, CoCl
2, NiCl
2, ZrCl
4, TiF
3, TiF
4, TiCl
3, TiCl
4, TiI
4, VF
3, VF
4, VF
5, VCl
3, VCl
4, VBr
3, YCl
3, NbF
5, NbCl
5, MoCl
3, MoCl
5, MoF
6, RuBr
3, RuI
3, RhCl
3, HfCl
4, PdCl
2, PtCl
2, PtCl
4, LaCl
3, CeF
3And CeCl
4One or more.
As most preferably, above-mentioned catalyst of transition metal oxide is CoO, Co
2O
3, Co
3O
4, NiO, TiO
2, TiO, V
2O
5, Y
2O
3, Nb
2O
5, MoO
2, MoO
3, Ru
2O
3, HfO
2, PdO, PtO
2, La
2O
3, CeO
2One or more.
As preferably, above-mentioned catalyzer add-on is 0.1%～10% of start material hydrolith and a calcium boride gross weight.
As preferably, above-mentioned mechanicals efforts adopts mechanical ball milling, and the mass ratio of abrading-ball and sample is 10～120:1, and rotational speed of ball-mill is 200～600 rev/mins, and the ball milling time is 10～120 hours.
As preferably, the hydrogen pressure of described hydrogen atmosphere is 40～70 normal atmosphere.
The present invention compared with prior art, the useful effect that has is:
The present invention is under normal temperature and relatively low hydrogen pressure, through adding catalyzer and by the mechanical energy of mechanical ball milling, making hydrolith and calcium boride under solid conditions, hydrogenation take place, synthesizes hydroboration calcium.In building-up process, avoided adopting the organism such as expensive and deleterious boron triethyl that use in the liquid wet chemistry method that refluxes of hydrolith and triethylamine borine, avoided in the liquid phase method long-time stirring leaching, filtration required when being raw material, distilled operating process such as desolvate with alkali metal borohydride and calcium halide.Also avoided the reactor drum of the complex and expensive of required high temperature high pressure process of existing solid phase method and employing thereof.Advantages such as the present invention has compound method and equipment is simple, reaction process is controllable, reaction conditions is gentle, security is good.Because the part catalyzer that adopts in the synthetic hydroboration calcium process has katalysis to the hydrogen of putting of hydroboration calcium, thereby corresponding synthetic hydroboration calcium also has the good advantage of hydrogen desorption kinetics performance.This has positive meaning for hydroboration calcium as hydrogen storage material.
Description of drawings
Fig. 1 is CaH
2-CaB
6The FT-IR collection of illustrative plates of 48 hours products of ball milling under 60 bar hydrogen pressures.
Fig. 2 is CaB
6-CaH
2The FT-IR collection of illustrative plates of-5wt%Co 96 hours products of ball milling under 55 bar hydrogen pressures.
Fig. 3 is CaH
2-CaB
6The FT-IR collection of illustrative plates of-10wt%Ni 48 hours products of ball milling under 60 bar hydrogen pressures.
Fig. 4 is CaH
2-CaB
6-10wt%Ni under 60 bar hydrogen pressures 48 hours products of ball milling put the hydrogen curve.
Fig. 5 is CaH
2-CaB
6The FT-IR collection of illustrative plates of-10wt%Mo 48 hours products of ball milling under 60 bar hydrogen pressures.
Fig. 6 is CaH
2-CaB
6-10wt%Mo under 60 bar hydrogen pressures 48 hours products of ball milling put the hydrogen curve.
Fig. 7 is CaH
2-CaB
6-6wt%TiF
4The FT-IR collection of illustrative plates of 72 hours products of ball milling under 50 bar hydrogen pressures.
Fig. 8 is CaH
2-CaB
6-8wt%ZrCl
4The FT-IR collection of illustrative plates of 36 hours products of ball milling under 55 bar hydrogen pressures.
Fig. 9 is CaH
2-CaB
6-10wt%TiF
424 hours products of ball milling puts the hydrogen curve under 60 bar hydrogen pressures.
Figure 10 is CaH
2-CaB
6-5wt%ZrCl
456 hours products of ball milling puts the hydrogen curve under 55 bar hydrogen pressures.
Figure 11 is CaH
2-CaB
6-7wt%TiO
2The FT-IR collection of illustrative plates of 72 hours products of ball milling under 40 bar hydrogen pressures.
The practical implementation method
In the glove box of argon gas atmosphere; With hydrolith and calcium boride 2:1 weighing in molar ratio; As initial reactant; And add in transition metal of the present invention, transition metal halide and the transition metal oxide one or more as catalyzer, in the ball grinder of packing into after the mixing, under the hydrogen atmosphere of certain pressure, carry out mechanical ball milling.The hydrogen pressure that wherein adopts during ball milling is 10 –, 150 normal atmosphere, and ball-to-powder weight ratio is (20 – 120): 1, and rotational speed of ball-mill is 600 rev/mins of 200 –, the ball milling time is 10 – 100 hours.The hydroboration calcium of preparation gained carries out structural characterization through Fourier's infared spectrum appearance (FT-IR), and tests its hydrogen discharging performance under differing temps.The test of institute's synthetic hydroboration calcium hydrogen discharging performance under differing temps through program temperature controller and pressure transmitter by corresponding computer software, the pressure of detection hydroboration calcium institute's release hydrogen under differing temps.
Embodiment 1
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, do not add any catalyzer, as control group, the stainless steel jar mill of packing into after the mixing.Charge into the atmospheric hydrogen of 60bar after ball grinder vacuumizes, seal ball grinder then.Ball grinder is placed on the planetary ball mill, with 500 rev/mins speed ball millings 48 hours.Fig. 1 is the FT-IR collection of illustrative plates of this milled product.2292,2225 cm
-1Faint B-H infrared signature absorption peak has appearred in the place, and 1189,1124 cm
-1The place does not occur.
Embodiment 2
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 5 wt.% Co, in the stainless steel jar mill of packing into after the mixing.After ball grinder vacuumized, charge into 55 atmospheric hydrogen, the sealing ball grinder.Ball grinder is placed on the planetary ball mill, with 500 rev/mins speed ball millings 96 hours.Fig. 2 is the FT-IR collection of illustrative plates of this milled product, 2292,2225,1189,1124 cm
-1The absorption peak at place has been explained the synthetic of hydroboration calcium.
Embodiment 3
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 10wt.%Ni, the stainless steel jar mill of packing into after the mixing.Charge into the atmospheric hydrogen of 60bar after ball grinder vacuumizes, seal ball grinder then.Ball grinder is placed on the planetary ball mill, with 500 rev/mins speed ball millings 48 hours.Fig. 3 is the FT-IR collection of illustrative plates of this milled product.2292,2225,1189,1124 cm
-1The absorption peak at place has been explained the synthetic of hydroboration calcium.Fig. 4 is put the hydrogen curve for milled product, and the initial hydrogen discharging temperature of sample is at 150 ℃.
Embodiment 4
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 10wt.%Mo, the stainless steel jar mill of packing into after the mixing.Charge into the atmospheric hydrogen of 60bar after ball grinder vacuumizes, seal ball grinder then.Ball grinder is placed on the planetary ball mill, with 400 rev/mins speed ball millings 48 hours.Fig. 5 is the FT-IR collection of illustrative plates of this milled product.2292,2225,1189,1124 cm
-1The absorption peak at place has been explained the synthetic of hydroboration calcium.Fig. 6 is put the hydrogen curve for milled product, and the initial hydrogen discharging temperature of sample is at 150 ℃.
Embodiment 5
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 6wt.%TiF
4, in the stainless steel jar mill of packing into after the mixing.After ball grinder vacuumized, charge into 50 atmospheric hydrogen, the sealing ball grinder.Again ball grinder is placed on the planetary ball mill, with 500 rev/mins speed ball millings 72 hours.Fig. 7 is the FT-IR collection of illustrative plates of this milled product.2292,2225,1189,1124 cm
-1The absorption peak at place has been explained the synthetic of hydroboration calcium.
Embodiment 6
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 8wt.%ZrCl
4, the stainless steel jar mill of packing into after the mixing.Again ball grinder is vacuumized, charge into 55 atmospheric hydrogen, the sealing ball grinder.Again ball grinder is placed on the planetary ball mill, with 400 rev/mins speed ball millings 36 hours.Fig. 8 is the FT-IR collection of illustrative plates of this milled product.2292,2225,1189,1124 cm
-1The absorption peak at place has been explained the synthetic of hydroboration calcium.
Embodiment 7
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 10wt.%TiF
4, the stainless steel jar mill of packing into after the mixing.Again ball grinder is vacuumized, charge into 60 atmospheric hydrogen, the sealing ball grinder.Again ball grinder is placed on the planetary ball mill, with 400 rev/mins speed ball millings 24 hours.Fig. 9 is put the hydrogen curve for this milled product, and the initial hydrogen discharging temperature of sample is at 150 ℃.GIF in the mechanical milling process
4Introducing, improved the hydrogen desorption kinetics performance of synthetic hydroboration calcium, make its initial hydrogen discharging temperature low than the theoretical hydrogen discharging temperature of hydroboration calcium, this for hydroboration calcium the most hydrogen storage material have positive meaning.
Embodiment 8
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 5wt.%ZrCl
4, go in the stainless steel jar mill after the mixing.Charge into 55 atmospheric hydrogen after ball grinder vacuumizes, then ball grinder is sealed.Ball grinder is placed on the planetary ball mill, with 300 rev/mins speed ball millings 56 hours.Figure 10 is put the hydrogen curve for this milled product, and the initial hydrogen discharging temperature of sample has been explained the synthetic of hydroboration calcium at 180 ℃.The synthetic material has with respect to the low initial hydrogen discharging temperature of the theoretical hydrogen discharging temperature of hydroboration calcium, and this has positive meaning for hydroboration calcium as hydrogen storage material.
Embodiment 9
In the glove box of argon gas atmosphere, take by weighing hydrolith and calcium boride with mol ratio 2:1, and add 7wt.%TiO
2, the stainless steel jar mill of packing into after the mixing.Charge into 40 atmospheric hydrogen after ball grinder vacuumizes, seal ball grinder then.Ball grinder is placed on the planetary ball mill, with 300 rev/mins speed ball millings 72 hours.Figure 11 is the FT-IR collection of illustrative plates of this milled product.2292,2225,1189,1124 cm
-1The absorption peak at place has been explained the synthetic of hydroboration calcium.
Claims (5)
1. the method for the synthetic hydroboration calcium of a normal temperature solid phase ball milling; It is characterized in that: this method is in 40～70 atmospheric hydrogen atmospheres at hydrogen pressure; Under the normal temperature condition with hydrolith and calcium boride as start material matter; Adopting transition metal is that catalyzer reacts under the effect of mechanicals efforts and makes, and the catalyzer add-on is 5%～10% of start material hydrolith and a calcium boride gross weight; Described mechanicals efforts adopts mechanical ball milling, and the mass ratio of abrading-ball and sample is 10～120:1, and rotational speed of ball-mill is 200～600 rev/mins, and the ball milling time is 10～120 hours; Its chemical equation is following:
2. the method for the synthetic hydroboration calcium of a kind of normal temperature solid phase ball milling according to claim 1, it is characterized in that: transition metal is one or more among Fe, Co, Ni, Zr, Ti, V, Nb, Mo, Ru, Pd, Pt, Rh and the Hf.
3. the method for the synthetic hydroboration calcium of a kind of normal temperature solid phase ball milling according to claim 2, it is characterized in that: catalyzer is selected one or more in transition metal simple substance, transition metal halide and the transition metal oxide for use.
4. the method for the synthetic hydroboration calcium of a kind of normal temperature solid phase ball milling according to claim 3, it is characterized in that: transition metal halide catalyst is FeCl
3, CoCl
2, NiCl
2, ZrCl
4, TiF
3, TiF
4, TiCl
3, TiCl
4, TiI
4, VF
3, VF
4, VF
5, VCl
3, VCl
4, VBr
3, NbF
5, NbCl
5, MoCl
3, MoCl
5, MoF
6, RuBr
3, RuI
3, RhCl
3, HfCl
4, PdCl
2, PtCl
2And PtCl
4One or more.
5. the method for the synthetic hydroboration calcium of a kind of normal temperature solid phase ball milling according to claim 3, it is characterized in that: catalyst of transition metal oxide is CoO, Co
2O
3, Co
3O
4, NiO, TiO
2, TiO, V
2O
5, Nb
2O
5, MoO
2, MoO
3, Ru
2O
3, HfO
2, PdO and PtO
2One or more.
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Citations (1)
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|---|---|---|---|---|
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
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|---|---|---|---|---|
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
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