CN108545699B - Method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling - Google Patents
Method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling Download PDFInfo
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- CN108545699B CN108545699B CN201810286315.5A CN201810286315A CN108545699B CN 108545699 B CN108545699 B CN 108545699B CN 201810286315 A CN201810286315 A CN 201810286315A CN 108545699 B CN108545699 B CN 108545699B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The invention discloses a method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling, which comprises the steps of carrying out solid-phase ball milling on a mixture of a reducing agent, a sodium supplement agent and a reduced material by a ball mill under the room-temperature condition, and purifying to obtain sodium borohydride; the reducing agent comprises more than one of magnesium, magnesium hydride, aluminum, calcium silicide and magnesium silicide; the sodium supplement agent comprises more than one of sodium hydroxide, sodium hydride and sodium carbonate; the reduced material is sodium tetraborate or sodium tetraborate containing crystal water, or a mixture of sodium tetraborate and sodium tetraborate containing crystal water; the solid phase ball milling is carried out in the mixed atmosphere of argon and hydrogen, or in the argon atmosphere or hydrogen atmosphere. The invention has the advantages of short production flow, mild reaction conditions, low cost, high yield, no pollution, high safety factor and easy industrial production.
Description
Technical Field
The invention relates to a preparation method of sodium borohydride, in particular to a method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling.
Background
The application of hydrogen energy is restricted by the storage technology, the hydrogen production and hydrogen storage are integrated by the hydrolysis hydrogen production technology, and the problem of hydrogen storage is hopefully solved by the hydrolysis hydrogen production of sodium borohydride. Sodium borohydride is a traditional complex hydride, and has high hydrogen storage capacity, large hydrogen release capacity for hydrolysis (theoretical hydrogen release capacity can reach 10.8 wt%), controllable hydrolysis reaction, high purity of produced hydrogen, and no toxicity and harm of hydrolysis byproducts. However, sodium borohydride is not a substance directly existing in nature, and the hydrolysis reaction is not reversible, and the byproduct is difficult to reduce back to sodium borohydride at low cost, so if sodium borohydride is used for hydrogen production through hydrolysis, a proper method for preparing and regenerating sodium borohydride is needed.
As for the regeneration method, mainly aimed at sodium metaborate, which is a byproduct of the hydrolysis of sodium borohydride, a suitable method has been mentioned in patent 201610835517.1; however, the preparation method is different because the preparation of sodium borohydride mainly aims at how to obtain sodium borohydride from nature, and is a process using borax, which is complementary to the process described in the above patent, and the existing method for preparing sodium borohydride has industrial method and laboratory method.
At present, the commercial production method of sodium borohydride mainly comprises a Schlesinger method and a Bayer method, and the two main production processes are as follows: the reaction equation of the Schlesinger method is as follows:
4NaH+B(OCH3)3→NaBH4+3NaOCH3(1)
h prepared by reforming raw material NaH with metallic Na and natural gas2Obtained by reaction, B (OCH)3)3Then reacting borax with sulfuric acid to obtain boric acid, and then reacting with methanol to obtain the product. The production condition of the Schlesinger method is that the reaction is carried out at 225-275 ℃, the reaction temperature is moderate, but the amount of NaH used as a reducing agent is large, so that the cost is difficult to further reduce.
The reaction equation for the Bayer process is as follows:
Na2B4O7+16Na+8H2+7SiO2→4NaBH4+7Na2SiO3(2)
wherein Na2B4O7Is prepared by dehydrating natural borax. The Bayer process has the production condition that the high-temperature reaction at 700 ℃ is carried out under the high-pressure hydrogen atmosphere, and the reaction condition is higher. The Bayer process uses a large amount of Na as a reducing agent and H derived from reforming natural gas2Increasing the final synthesis cost.
In conclusion, the current method for industrially producing sodium borohydride has higher cost. The boron source of the methods is borax, but the use process needs additional steps to convert the borax into anhydrous borax by removing water, and the process is more complicated; the hydrogen source is natural gas or petroleum, and the process is also complex and difficult to continuously use. Therefore, the requirements of practical hydrolysis hydrogen production application are difficult to meet.
According to international reports (Journal of Alloys and Compounds,2003,349, 232-:
8MgH2+Na2B4O7+Na2CO3→4NaBH4+8MgO+CO2(3)
9MgH2+Na2B4O7+2NaOH→4NaBH4+9MgO+2H2(4)
9MgH2+Na2B4O7+Na2O2→4NaBH4+9MgO+H2(5)
4MgH2+Na2B4O7→2NaBH4+4MgO+B2O3(6)
the reaction is carried out in the high-energy ball milling process, the reaction condition is normal temperature and normal pressure, and the problems of cost, energy consumption and safety caused by high temperature and high pressure in the Bayer process are solved. But more importantly, the method uses magnesium hydride with high price as a reducing agent, and the magnesium hydride is high in price, and the production of the magnesium hydride requires magnesium and hydrogen to be synthesized at high temperature and high pressure, so that the energy consumption is high, and an additional hydrogen source is used; the boron source used in the method is anhydrous borax, the natural borax needs to be prepared by removing water, the water removing temperature is higher than 400 ℃, and the energy consumption in the preparation process is large. Therefore, the existing method for preparing sodium borohydride in a laboratory has high cost and large energy consumption, and is difficult to be practically applied to industrial production.
In summary, the existing sodium borohydride production and regeneration methods have high requirements on preparation conditions and high production cost, which makes the method for preparing hydrogen by hydrolyzing commercial sodium borohydride difficult to be applied in large scale due to cost, and needs to find additional hydride or hydrogen source to supplement hydrogen during preparation, thus increasing the cost.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling, which directly synthesizes the sodium borohydride by borax in one step, and has mild preparation conditions and simple process.
The purpose of the invention is realized by the following technical scheme:
the method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling comprises the steps of carrying out solid-phase ball milling on a reducing agent, a sodium supplement agent and a reduced material by a ball mill at room temperature, and purifying to obtain sodium borohydride;
the reducing agent comprises more than one of magnesium, magnesium hydride, aluminum, calcium silicide and magnesium silicide;
the sodium supplement agent comprises more than one of sodium hydroxide, sodium hydride and sodium carbonate;
the reduced material is sodium tetraborate or sodium tetraborate containing crystal water, or a mixture of sodium tetraborate and sodium tetraborate containing crystal water;
the solid phase ball milling is carried out in a non-oxidizing atmosphere.
Assuming that the molar weight of the magnesium element in the reducing agent is n1The molar amount of the aluminum element is n2The molar amount of the calcium element is n3(ii) a Wherein n is1≥0，n2≥0，n3≥0；
Setting the number of oxygen in the reduced material as a;
then:
(n1+1.5n2+n3):a＝(9:10)～(30:17)。
the molar ratio of the sodium supplement agent to the reduced material is (6:1) - (1: 1).
The non-oxidizing atmosphere is a mixed atmosphere of argon and hydrogen, or an argon atmosphere, or a hydrogen atmosphere or vacuum.
The pressure of the mixed atmosphere of argon and hydrogen is 0-2 MPa; the pressure of the argon atmosphere is 0-2 MPa; the pressure of the hydrogen atmosphere is 0-2 MPa.
The ball mill is a high-energy pendulum vibration ball mill.
The ball-milling ball-material ratio is 5-50: 1; the ball milling time is 1h-20 h; the rotation speed of the ball mill is 1000-1200 r/min.
The purification specifically comprises the following steps:
and dissolving the mixture subjected to ball milling by using ethylenediamine, filtering to obtain clear filtrate, and drying the filtrate to obtain pure sodium borohydride powder.
The drying is vacuum drying.
The sodium tetraborate containing crystal water is sodium tetraborate decahydrate or sodium tetraborate pentahydrate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention realizes the mechanochemical process by means of high-energy ball milling at normal temperature and normal pressure, directly uses a main boron source (sodium tetraborate pentahydrate or sodium tetraborate decahydrate or a mixture of sodium tetraborate and sodium tetraborate containing crystal water) and a reducing agent material (one or more of magnesium, magnesium hydride, aluminum, calcium calcified or magnesium silicide) in nature, and reacts to synthesize the sodium borohydride under the solid condition. The mechanical ball milling method adopted by the invention avoids the high-temperature and high-pressure synthesis process of the Schlesinger method and the Bayer method, the reaction process is controllable and adjustable, the process is simple, the energy consumption is low, the yield is high, no pollution is caused, the mechanical ball milling method is an industrially mature and common method, the mass production of the sodium borohydride is easy to realize, and the yield of the sodium borohydride synthesized by the method can reach 95%, namely the method has the technical condition of realizing high-efficiency mass production.
(2) The boron source used in the invention is borax, which is one of the main boron sources in nature and a commonly used boron compound, and the traditional laboratory method needs to dehydrate the borax at a high temperature of more than 400 ℃ to prepare anhydrous sodium tetraborate, and the process needs high energy consumption and high cost. The invention completely omits the dehydration process and directly produces the sodium borohydride.
(3) The invention directly uses the positive hydrogen carried by the crystal water in the borax as the hydrogen source of the negative hydrogen in the sodium borohydride, and compared with the traditional laboratory method, the invention does not need to use hydrogen or hydride and the like as additional hydrogen sources to provide hydrogen. That is, the positive hydrogen ions in the crystal water in the mixture of sodium tetraborate pentahydrate or decahydrate or sodium tetraborate with sodium tetraborate containing crystal water are reduced to the negative hydrogen ions in the sodium borohydride that can be used portably. The invention relates to an integrated synthesis method for preparing and storing hydrogen. The method has positive significance for sodium borohydride as hydrogen production and storage materials.
(4) The raw materials of magnesium, aluminum, calcium silicide or magnesium silicide or the alloy of the magnesium, the aluminum, the calcium silicide or the magnesium silicide are low in price and suitable for mass production. While magnesium hydride is only one auxiliary raw material that can be added.
Drawings
FIG. 1 is an XRD pattern of a ball milled product of magnesium, sodium carbonate and sodium tetraborate decahydrate, example 1 of the present invention.
FIG. 2 is an XRD pattern of a ball milled product of magnesium hydride, sodium hydride and sodium tetraborate pentahydrate of example 7 of the present invention.
Fig. 3 is an XRD pattern of ball-milled product of magnesium silicide and sodium tetraborate decahydrate according to an embodiment of the present invention, wherein the corresponding embodiments of the lines are: (a) example 12; (b) example 17.
FIG. 4 is an FTIR spectra of ball milled products of calcium silicide, sodium hydride and sodium tetraborate pentahydrate of example 19 of the present invention.
Fig. 5 is an XRD pattern of a ball milled product of calcium silicide and sodium tetraborate decahydrate according to an embodiment of the present invention, wherein the various lines correspond to the embodiments: (a) example 22; (b) example 23.
FIG. 6 is an XRD pattern of a ball milled product of aluminum, sodium hydroxide and sodium tetraborate pentahydrate from example 24 of the present invention.
FIG. 7 is an XRD pattern of purified sodium borohydride in accordance with an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The specific purification process is not specifically described in the examples, but the following methods are used: in a glove box under argon atmosphere, dissolving the ball-milled mixture by using ethylenediamine, filtering to obtain clear filtrate, drying the filtrate in vacuum to obtain pure sodium borohydride powder, and finally quantitatively obtaining the yield by using an iodine titration method. Examples the target product characterization was analyzed by fourier infrared spectroscopy (FT-IR) or X-ray diffractometry (XRD).
The ball milling in the examples was carried out at room temperature.
Example 1
In a glove box under argon atmosphere at 0.1MPa, the molar ratio 28: 1:1 weighing magnesium, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and mixing the ballsThe milling pot was placed in a high energy pendulum vibration ball mill (QM-3C) with a ball to feed ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. FIG. 1 is an XRD spectrum of the ball-milled product, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to obtain a clear filtrate, and the filtrate was vacuum dried to obtain a white powder, fig. 6 shows the XRD pattern of the white powder, and diffraction peaks appearing at 25.1,28.9,41.4,49.0,51.3,60.0,66.0, and 68.0 ° belong to sodium borohydride crystals, thus proving that the white powder is pure sodium borohydride, and the quantitative yield by iodometry is 63%. The price of Mg as raw material is about 12000 yuan/ton, and in the closest technology, the raw material MgH2The price is about 800000 yuan/ton, and only the price of the raw material is calculated by using the method and is reduced remarkably.
Example 2
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 22: 1: weighing magnesium, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 30: 1, ball milling rotation speed is 1000 r/min, and ball milling is directly carried out for 10h in the argon atmosphere. The XRD pattern is similar to that of figure 1, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 42% by iodometric titration.
Example 3
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 1: weighing magnesium, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 5: 1, ball milling rotation speed of 1000 r/min, and directly ball milling for 5h in the argon atmosphere. The XRD pattern is similar to that of figure 1, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 21% by iodometric titration.
Example 4
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 23: 1:1, weighing magnesium, sodium carbonate and sodium borate pentahydrate, mixing, filling into a ball milling tank, vacuumizing, filling 2MPa hydrogen, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. The XRD pattern is similar to that of figure 1, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 52% by iodometric titration.
Example 5
In a glove box under argon atmosphere at 0.1MPa, the molar ratio 28: 2: weighing magnesium, sodium hydroxide and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. The XRD pattern is similar to that of figure 1, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder which was confirmed to be pure sodium borohydride with a 59% quantitative yield by iodometric titration.
Example 6
In a glove box under argon atmosphere at 0.1MPa, the molar ratio 28: 2: weighing magnesium, sodium hydride and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. The XRD pattern is similar to that of figure 1, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder, which was confirmed to be pure sodium borohydride with a quantitative yield of 61% by iodometric titration.
Example 7
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 15: 2: weighing magnesium hydride, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly ball milling for 5h in the argon atmosphere. FIG. 2 is an XRD spectrum of the ball-milled product, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder, which was confirmed to be pure sodium borohydride with a quantitative yield of 96% by iodometric titration.
Example 8
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 13: 2: weighing magnesium hydride, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 30: 1, ball milling rotation speed is 1000 r/min, and ball milling is directly carried out for 2h in the argon atmosphere. The XRD pattern is similar to that of figure 2, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder, which was confirmed to be pure sodium borohydride with a quantitative yield of 72% by iodometric titration.
Example 9
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 2: weighing magnesium hydride, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 5: 1, ball milling rotation speed is 1000 r/min, and ball milling is directly carried out for 1h in the argon atmosphere. The XRD pattern is similar to that of figure 2, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder which was confirmed to be pure sodium borohydride with 53% quantitative yield by iodometric titration.
Example 10
In a glove box under argon atmosphere at 0.1MPa, the molar ratio 28: 2: weighing magnesium hydride, sodium hydride and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, vacuumizing, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed is 1000 r/min, and ball milling is directly carried out for 2h in the argon atmosphere. The XRD pattern is similar to that of figure 2, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 87% by iodometric titration.
Example 11
In a glove box under argon atmosphere at 0.1MPa, the molar ratio 28: 2: weighing magnesium hydride, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 5h in the argon atmosphere. The XRD pattern is similar to that of figure 2, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder which was confirmed to be pure sodium borohydride with a quantitative yield of 88% by iodometric titration.
Example 12
In a glove box under argon atmosphere at 0.1MPa, the molar ratio 28: 2: weighing magnesium hydride, sodium hydroxide and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 5h in the argon atmosphere. The XRD pattern is similar to that of figure 2, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder, which was confirmed to be pure sodium borohydride with a quantitative yield of 85% by iodometric titration.
Example 13
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 1: weighing magnesium silicide, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. FIG. 3, Curve a, is the XRD pattern of the ball-milled product, in which diffraction peaks appearing at 25.1,28.9,41.4 degrees belong to sodium borohydride crystals, which proves that the sodium borohydride crystals are generated; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a yield of 74% by iodometric titration. Raw material Mg2The price of Si is about 11000 yuan/ton, and in the closest technology, the raw material MgH2The price is about 800000 yuan/ton, and only the price of the raw material is calculated by using the method and is reduced remarkably.
Example 14
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 11: 1: weighing magnesium silicide, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 30: 1, ball milling rotation speed is 1000 r/min, and ball milling is directly carried out for 10h in the argon atmosphere. The XRD pattern is similar to the curve a in figure 3, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 56% by iodometric titration.
Example 15
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 9: 1: weighing magnesium silicide, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 5: 1, ball milling rotation speed of 1000 r/min, and directly ball milling for 5h in the argon atmosphere. The XRD pattern is similar to the curve a in figure 3, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 35% by iodometric titration.
Example 16
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 1: weighing magnesium silicide, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, vacuumizing, filling into a mixed atmosphere (argon and hydrogen are mixed) of 0.1MPa, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. The XRD pattern is similar to the curve a in figure 3, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 69% by iodometric titration.
Example 17
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 2: weighing magnesium silicide, sodium hydroxide and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. FIG. 3, curve b is the XRD spectrum of the ball-milled product, and the diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, which proves that the sodium borohydride crystals are generated; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 65% by iodometric titration.
Example 18
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 6: weighing magnesium silicide, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. The XRD pattern is similar to the curve b in figure 3, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 69% by iodometric titration.
Example 19
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 16.5: 5: 1, weighing calcium silicide, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. FIG. 4 is an FTIR spectrum of the ball-milled product, wherein diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, which proves that the sodium borohydride crystals are generated; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 44% by iodometric titration. Raw material CaSi2The price is 16250 yuan/ton, and in the closest technology, the raw material MgH2The price is about 800000 yuan/ton, and only the price of the raw material is calculated by using the method and is reduced remarkably.
Example 20
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 5: 1, weighing calcium silicide, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 30: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The FTIR spectrum is similar to that in figure 4, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 28% by iodometric titration.
Example 21
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 5: 1, weighing calcium silicide, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 5: 1, ball milling rotation speed of 1200 r/min, and ball milling for 5h in the argon atmosphere. The FTIR spectrum is similar to that in figure 4, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 15% by iodometric titration.
Example 22
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 22.5: 1:1, weighing calcium silicide, sodium hydroxide and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. FIG. 5, Curve a, is the XRD pattern of the ball-milled product, in which the diffraction peak appearing at 28.9 degrees belongs to sodium borohydride crystal, thus proving the generation of sodium borohydride crystal; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 41% by iodometric titration.
Example 23
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 22.5: 1:1, weighing calcium silicide, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. FIG. 5, curve b is the XRD pattern of the ball-milled product, and the diffraction peaks appearing at 28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, which proves that the sodium borohydride crystals are generated; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 42% by iodometric titration.
Example 24
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 20: 6: weighing aluminum, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. FIG. 6 is an XRD spectrum of the ball-milled product, and diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in the curve belong to sodium borohydride crystals, which proves that the hydroborationSodium crystal generation; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 33% by iodometric titration. The price of Al as raw material is about 14210 yuan/ton, while in the closest technique, MgH as raw material2The price is about 800000 yuan/ton, and only the price of the raw material is calculated by using the method and is reduced remarkably.
Example 25
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 17: 6: weighing aluminum, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 30: 1, ball milling rotation speed is 1000 r/min, and ball milling is directly carried out for 10h in the argon atmosphere. The XRD pattern is similar to that of figure 6, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 21% by iodometric titration.
Example 26
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 11: 6: weighing aluminum, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 5: 1, ball milling rotation speed of 1000 r/min, and directly ball milling for 5h in the argon atmosphere. The XRD pattern is similar to that of figure 6, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 7% by iodometric titration.
Example 27
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 20: 6:1, weighing aluminum, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, vacuumizing, filling 0.1MPa hydrogen, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. The XRD pattern is similar to that of figure 6, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 30% by iodometric titration.
Example 28
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 21: 2: weighing aluminum, sodium hydride and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. The XRD pattern is similar to that of figure 6, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 14% by iodometric titration.
Example 29
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 21: 1: weighing aluminum, sodium carbonate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and ball milling for 20h in the argon atmosphere. The XRD pattern is similar to that of figure 6, diffraction peaks appearing at 25.1,28.9 and 41.4 degrees in a curve belong to sodium borohydride crystals, and the generation of the sodium borohydride crystals is proved; the mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 12% by iodometric titration.
Example 30
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 4: 1: weighing magnesium, magnesium hydride, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 72% by iodometric titration.
Example 31
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 2: 1: weighing magnesium, magnesium hydride, sodium carbonate, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 70% by iodometric titration.
Example 32
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 9: 12: 1: weighing magnesium, magnesium silicide, sodium hydride, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a 58% yield by iodometric titration.
Example 33
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 12: 1: weighing magnesium, calcium silicide, sodium hydride, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 48% by iodometric titration.
Example 34
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 12: 1: weighing magnesium, aluminum, sodium hydroxide, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 34% by iodometric titration.
Example 35
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 9: 2: 1: weighing magnesium hydride, magnesium silicide, sodium carbonate, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 76% by iodometric titration.
Example 36
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 2: 1: weighing magnesium hydride, calcium silicide, sodium carbonate, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 61% by iodometric titration.
Example 37
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 2: 1: weighing magnesium hydride, aluminum, sodium hydroxide, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a 58% yield by iodometric titration.
Example 38
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 2: 1: weighing magnesium hydride, aluminum, sodium carbonate, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 60% by iodometric titration.
Example 39
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 9: 18: 12: 1: weighing magnesium silicide, calcified silicon, sodium hydride, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 44% by iodometric titration.
Example 40
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 9: 18: 2: 1: weighing magnesium silicide, aluminum, sodium hydroxide, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 39% by iodometric titration.
EXAMPLE 41
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 18: 2: 1:1, weighing calcium silicide, aluminum, sodium hydroxide, sodium tetraborate decahydrate and anhydrous sodium tetraborate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 32% by iodometric titration.
Example 42
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 12: 6: 1: 2: 2 weighing magnesium, magnesium hydride, magnesium silicide, sodium carbonate, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 69% by iodometric titration.
Example 43
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 6: 12: 1: 2: 2 weighing magnesium, magnesium silicide, calcium silicide, sodium carbonate, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 52% by iodometric titration.
Example 44
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 12: 12: 2: 2: 2 weighing magnesium, calcium silicide, aluminum, sodium hydroxide, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 42% by iodometric titration.
Example 45
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 6: 12: 1: 2: weighing magnesium hydride, magnesium silicide, calcium silicide, sodium carbonate, sodium hydride and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 65% by iodometric titration.
Example 46
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 6: 12: 1: 2: weighing magnesium hydride, calcium silicide, aluminum, sodium carbonate, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 52% by iodometric titration.
Example 47
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 6: 12: 12: 1: 2: 2 weighing magnesium silicide, calcium silicide, aluminum, sodium carbonate, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 44% by iodometric titration.
Example 48
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 12: 12: 1: 2: 2 weighing magnesium, magnesium hydride, aluminum, sodium carbonate, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 56% by iodometric titration.
Example 49
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 6: 12: 2: 2: weighing magnesium hydride, magnesium silicide, aluminum, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a yield of 67% by iodometric titration.
Example 50
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 12: 6: 12: 2: 2: 2 weighing magnesium, magnesium silicide, aluminum, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 48% by iodometric titration.
Example 51
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 7: 14: 14: 1: 2: 2: weighing magnesium hydride, magnesium silicide, calcium silicide, aluminum, sodium carbonate, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-to-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 55% by iodometric titration.
Example 54
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 7: 14: 14: 1: 2: 2: 3, weighing magnesium, magnesium silicide, calcium silicide, aluminum, sodium carbonate, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-to-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 48% by iodometric titration.
Example 55
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 14: 14: 14: 1: 2: 2: 3 weighing magnesium, magnesium hydride, calcium silicide, aluminum, sodium carbonate, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-to-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 53% by iodometric titration.
Example 56
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 14: 7: 14: 1: 2: 2: 3 weighing magnesium, magnesium hydride, magnesium silicide, aluminum, sodium carbonate, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-to-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 57% by iodometric titration.
Example 57
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 14: 14: 14: 14: 1: 2: 2: 3 weighing magnesium, magnesium hydride, magnesium silicide, calcium silicide, sodium carbonate, sodium hydride, sodium hydroxide and sodium tetraborate pentahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-to-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 63% by iodometric titration.
Example 58
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 22: 22: 11: 22: 22: 2: 4: 4: 3: 3, weighing magnesium, magnesium hydride, magnesium silicide, calcium silicide, aluminum, sodium carbonate, sodium hydride, sodium hydroxide, anhydrous sodium tetraborate and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-to-material ratio of 50: 1, ball milling rotation speed of 1200 r/min, and directly performing ball milling for 10h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 55% by iodometric titration.
Comparative example
In a glove box under 0.1MPa argon atmosphere, the molar ratio of 18: 1, weighing magnesium and sodium tetraborate decahydrate, mixing, filling into a ball milling tank, and placing the ball milling tank into a high-energy pendulum vibration type ball mill (QM-3C) according to a ball-material ratio of 50: 1, ball milling rotation speed of 1000 r/min, and directly performing ball milling for 20h in the argon atmosphere. The mixture was dissolved using ethylenediamine and filtered to give a clear filtrate, which was dried under vacuum to give a white powder with a quantitative yield of 26% by iodometric titration.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The method for directly synthesizing the sodium borohydride by room-temperature solid-phase ball milling is characterized in that a reducing agent, a sodium supplement agent and a reduced material are subjected to solid-phase ball milling by a ball mill under the room-temperature condition, and the sodium borohydride is obtained after purification;
the reducing agent is magnesium hydride, the sodium supplement agent is sodium hydroxide, sodium hydride or sodium carbonate, and the reduced material is sodium tetraborate decahydrate or sodium tetraborate pentahydrate;
or the reducing agent is magnesium hydride and magnesium, the sodium supplement agent is sodium hydride or sodium carbonate, and the reduced material is a mixture of sodium tetraborate decahydrate and sodium tetraborate;
or the reducing agent is magnesium hydride and magnesium silicide, the sodium supplement agent is sodium carbonate, and the reduced material is a mixture of sodium tetraborate decahydrate and sodium tetraborate;
the solid phase ball milling is carried out in a non-oxidizing atmosphere.
2. The method for directly synthesizing sodium borohydride according to claim 1, wherein the molar weight of magnesium in the reducing agent is n1Wherein n is1＞0；
Setting the number of oxygen in the reduced material as a;
then: n is1:a=(9:10)~(30:17)。
3. The method for directly synthesizing the sodium borohydride by the room-temperature solid-phase ball milling is characterized in that the molar ratio of the sodium supplement agent to the reduced material is (6:1) - (1: 1).
4. The method for directly synthesizing sodium borohydride according to claim 1, characterized in that the non-oxidizing atmosphere is a mixed atmosphere of argon and hydrogen, or an argon atmosphere or a hydrogen atmosphere.
5. The method for directly synthesizing sodium borohydride according to claim 4, characterized in that the ball mill is a high-energy pendulum vibration ball mill.
6. The method for directly synthesizing sodium borohydride according to claim 4, characterized in that the ball-milling ratio of balls to materials is 5-50: 1; the ball milling time is 1h-20 h; the rotation speed of the ball mill is 1000-1200 r/min.
7. The method for directly synthesizing sodium borohydride by room temperature solid phase ball milling according to claim 1, wherein the purification specifically comprises:
and dissolving the mixture subjected to ball milling by using ethylenediamine, filtering to obtain clear filtrate, and drying the filtrate to obtain pure sodium borohydride powder.
8. The method for directly synthesizing sodium borohydride according to claim 7, characterized in that the drying is vacuum drying.
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| CN201810286315.5A CN108545699B (en) | 2018-04-03 | 2018-04-03 | Method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling |
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| CN201810286315.5A CN108545699B (en) | 2018-04-03 | 2018-04-03 | Method for directly synthesizing sodium borohydride by room-temperature solid-phase ball milling |
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| TWI741719B (en) * | 2019-08-06 | 2021-10-01 | 日商日本輕金屬股份有限公司 | Method for producing sodium borohydride |
| CN114436209B (en) * | 2022-03-08 | 2023-07-14 | 广东省科学院资源利用与稀土开发研究所 | Magnesium hydride-in-situ generated metal borohydride hydrolysis hydrogen production material and preparation method thereof |
| CN115159461B (en) * | 2022-06-28 | 2023-08-18 | 理道新材(北京)科技有限公司 | Preparation method of sodium borodeuteride |
| CN115159460A (en) * | 2022-07-14 | 2022-10-11 | 安徽泽升科技有限公司 | Preparation method of stable isotope reagent sodium boron deuteride |
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