CN115159461B - Preparation method of sodium borodeuteride - Google Patents
Preparation method of sodium borodeuteride Download PDFInfo
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- CN115159461B CN115159461B CN202210746136.1A CN202210746136A CN115159461B CN 115159461 B CN115159461 B CN 115159461B CN 202210746136 A CN202210746136 A CN 202210746136A CN 115159461 B CN115159461 B CN 115159461B
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- 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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Abstract
The invention belongs to the technical field of synthesis of deuterated compounds, and provides a preparation method of sodium borodeuteride. The preparation method of the invention takes boron-containing materials, diboron trioxide, sodium-containing compounds and metal deuterides as raw materials, and prepares the crude product of sodium boron deuteride with less impurities through one-step double decomposition reaction; the high-purity sodium boron deuteride can be obtained through extraction. Obviously, the preparation method provided by the invention has simple reaction steps and is suitable for industrial scale-up production. The data of the examples show that: the purity of the sodium borodeuteride prepared by the method is more than or equal to 99.95 percent, the deuteration rate is more than 99.5 percent, and the use requirement of downstream industry is met. Further, the metathesis reaction of the present invention can be carried out under ball milling conditions, which are relatively mild. Furthermore, in the preparation method provided by the invention, the crude sodium borodeuteride is purified by taking the organic amine as the extractant, so that no acid waste liquid is generated, and the post-treatment is simple.
Description
Technical Field
The invention relates to the technical field of deuterated compound synthesis, in particular to a preparation method of sodium borodeuteride.
Background
Deuterium is a stable, nonradioactive type of hydrogen that makes the chemical bond of the compound stronger. The deuterated pharmaceutical industry has grown vigorously since the first deuterated drug, tetrabenazine-d 6 (for the treatment of chorea, a non-voluntary dyskinesia) was approved by the U.S. food and drug administration (the U.S. food and Drug Administration, FDA). In some positions of the molecular structure of the medicine, deuterium atoms are used for exchanging hydrogen atoms, and the obtained modified medicine can inhibit the metabolic conversion to less active molecules or the steric mutation of enantiomers and diastereomers through the chemical change, so that the activity of the modified medicine is kept longer in vivo than that of a non-deuterated compound, and the service life of the medicine is prolonged.
Chinese patent publication No. CN105502292a discloses a method for preparing sodium borodeuteride by using stable isotope reagent, which comprises reacting boron compound, quartz sand and active metal at high temperature under deuterium atmosphere, and extracting and purifying to obtain sodium borodeuteride. In the method, sodium borodeuteride with purity more than 99.0% can be obtained through secondary purification, but the operation is complicated due to the secondary purification.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing sodium borodeuteride. The preparation method of the sodium borodeuteride provided by the invention is simple, and the purity of the obtained sodium borodeuteride is high.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of sodium borodeuteride, which comprises the following steps:
respectively calcining the boron-containing material and the boron trioxide to obtain a calcined boron-containing material and calcined boron trioxide;
mixing the calcined boron-containing material, calcined diboron trioxide, a sodium-containing compound and a metal deuteride, and carrying out double decomposition reaction under the condition of deuterium to obtain a sodium borodeuteride crude product;
extracting the sodium borodeuteride crude product, and drying the obtained extraction phase to obtain the sodium borodeuteride;
the boron-containing material comprises one or more of fibrous boron magnesium powder, natroborolysis powder and boron natralcite powder;
the sodium-containing compound comprises one or more of sodium deuteride sodium phenolate, sodium deuteride amino, sodium oxide and sodium deuteride ethanol;
the metal deuterides include one or more of lithium deuteride, titanium deuteride, sodium deuteride, zirconium deuteride, and aluminum tridentate.
Preferably, the molar quantity of boron element in the boron-containing material is a 1 The molar quantity of the sodium element is a 2 The method comprises the steps of carrying out a first treatment on the surface of the The molar quantity of boron element in the diboron trioxide is n; the molar quantity of sodium element in the sodium-containing compound is b; the molar weight of deuterium element in the metal deuteride is c;
a 1 、a 2 n, b and c satisfy the following relationship:
(a 2 +b)：(a 1 +n)＝(2～4)：1；
(a 1 +n)：c＝1：(5～10)。
preferably, the calcination temperature is independently 350-750 ℃ and the time is independently 3-6 h; the calcination is independently carried out under a protective atmosphere.
Preferably, the metathesis reaction is carried out under ball milling conditions; the ball-milling beads are zirconium oxide ball-milling beads, and the mass ratio of the zirconium oxide ball-milling beads to the diboron trioxide is (10-20): 1, the zirconia ball-milling beads are prepared from zirconia ball-milling beads with the diameter of 5mm, zirconia ball-milling beads with the diameter of 3mm and zirconia ball-milling beads with the diameter of 1mm according to the mass ratio of (1-2): (2-3): 1.
Preferably, the metathesis reaction is carried out at a temperature of 300 to 400 ℃ for a time of 4 to 10 hours.
Preferably, the extracting agent of the extraction is an organic amine; the organic amine comprises one or more of n-propylamine, n-butylamine, cyclohexylamine, ethylenediamine, triethylamine and aniline.
Preferably, the mass ratio of the extracted extractant to the sodium borodeuteride crude product is (2-10): 1.
preferably, the drying mode is freeze drying, and the time of freeze drying is 12-24 h.
Preferably, the particle size of the diboron trioxide is less than 100nm.
The invention provides a preparation method of sodium borodeuteride, which comprises the following steps: respectively calcining the boron-containing material and the boron trioxide to obtain a calcined boron-containing material and calcined boron trioxide; mixing the calcined boron-containing material, calcined diboron trioxide, a sodium-containing compound and a metal deuteride, and carrying out double decomposition reaction under the condition of deuterium to obtain a sodium borodeuteride crude product; extracting the sodium borodeuteride crude product, and drying the obtained extraction phase to obtain the sodium borodeuteride; the boron-containing material comprises one or more of fibrous boron magnesium powder, natroborolysis powder and boron natralcite powder; the sodium-containing compound comprises one or more of sodium deuteride sodium phenolate, sodium deuteride amino, sodium oxide and sodium deuteride ethanol; the metal deuterides include one or more of lithium deuteride, titanium deuteride, sodium deuteride, zirconium deuteride, and aluminum tridentate.
The preparation method provided by the invention takes boron-containing materials, diboron trioxide, sodium-containing compounds and metal deuterides as raw materials, and the crude product of the sodium boron deuteride with less impurities can be prepared through one-step double decomposition reaction; the high-purity sodium boron deuteride can be obtained through extraction. The preparation method provided by the invention has simple reaction steps and is suitable for industrial scale-up production. The data of the examples show that: the purity of the sodium borodeuteride prepared by the method is more than or equal to 99.5%, the deuteration rate is more than 99.5%, and the use requirement of downstream industries is met.
Further, the metathesis reaction of the present invention can be carried out under ball milling conditions, which are relatively mild.
Furthermore, in the preparation method provided by the invention, the crude sodium borodeuteride is purified by taking the organic amine as the extractant, so that no acid waste liquid is generated, and the post-treatment is simple.
Drawings
FIG. 1 is an XRD spectrum of sodium borodeuteride obtained in example 1.
Detailed Description
The invention provides a preparation method of sodium borodeuteride, which comprises the following steps:
respectively calcining the boron-containing material and the boron trioxide to obtain a calcined boron-containing material and calcined boron trioxide;
mixing the calcined boron-containing material, calcined diboron trioxide, a sodium-containing compound and a metal deuteride, and carrying out double decomposition reaction under the condition of deuterium to obtain a sodium borodeuteride crude product;
extracting the sodium borodeuteride crude product, and drying the obtained extraction phase to obtain the sodium borodeuteride;
the boron-containing material comprises one or more of fibrous boron magnesium powder, natroborolysis powder and boron natralcite powder;
the sodium-containing compound comprises one or more of sodium deuteride sodium phenolate, sodium deuteride amino, sodium oxide and sodium deuteride ethanol;
the metal deuterides include one or more of lithium deuteride, titanium deuteride, sodium deuteride, zirconium deuteride, and aluminum tridentate.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention respectively calcines the boron-containing material and the boron trioxide to obtain a calcined boron-containing material and a calcined boron trioxide.
In the present invention, the boron-containing material comprises fibrous boron magnesium powder (Mg 2 B 2 O 5 )、Natroborolysis powder (NaCaB) 3 B 2 O 7 (OH) 4 ·6H 2 O) and ground limestone boron (BCaNaO) 3 ) One or more of the following. In the present invention, the particle size of the boron-containing material is preferably 50 to 100. Mu.m.
In the present invention, the particle size of the diboron trioxide is preferably less than 100nm, more preferably 50 to 80nm.
In the present invention, the temperature of the calcination of the boron-containing material is preferably 350 to 750 ℃, more preferably 450 to 650 ℃, still more preferably 500 to 600 ℃; the time is preferably 3 to 6 hours, more preferably 4 to h; the calcination of the boron-containing material is preferably carried out under a protective atmosphere, which preferably comprises argon. After the boron-containing material is calcined, the invention preferably further comprises cooling to 25-30 ℃ under a protective atmosphere.
In the present invention, the temperature, time and atmosphere of the calcination of the diboron trioxide preferably correspond to the parameters of the calcination of the boron-containing material, and will not be described in detail herein. After the diboron trioxide is calcined, the invention preferably further comprises cooling to 25-30 ℃ under a protective atmosphere.
In the present invention, the calcination can remove adsorption and crystallization water of the boron-containing material and the diboron trioxide, preventing the introduction of hydrogen ions during the subsequent preparation process, resulting in a reduction of the deuteration rate of the final product.
After the calcined boron-containing material and the calcined diboron trioxide are obtained, the calcined boron-containing material, the calcined diboron trioxide, the sodium-containing compound and the metal deuteride are mixed, and double decomposition reaction is carried out under the deuterium condition to obtain a crude sodium borodeuteride product.
In the present invention, the sodium-containing compound includes one or more of sodium deuterated phenol, sodium deuterated amino, sodium oxide, and sodium deuterated ethoxide.
In the present invention, the metal deuteride includes one or more of lithium deuteride, titanium deuteride, sodium deuteride, zirconium deuteride, and aluminum tridentate.
In the invention, the molar quantity of boron element in the boron-containing material is a 1 The molar quantity of the sodium element is a 2 The method comprises the steps of carrying out a first treatment on the surface of the The said trioxidationThe molar quantity of boron element in diboron is n; the molar quantity of sodium element in the sodium-containing compound is b; the molar weight of deuterium element in the metal deuteride is c;
a 1 、a 2 preferably, n, b and c satisfy the following relationship:
(a 2 +b)：(a 1 +n) = (2 to 4): 1, more preferably (a) 2 +b)：(a 1 +n)＝3：1；
(a 1 +n): c=1: (5-10), more preferably (a) 1 +n): c=1: (6-9), more preferably (a) 1 +n)：c＝1：(7～8)。
In the present invention, the metathesis reaction is preferably carried out under ball milling conditions; the ball-milling balls of the ball mill are preferably zirconium oxide ball-milling balls; the mass ratio of the zirconia ball-milling beads to the diboron trioxide is preferably (10-20): 1, more preferably (11 to 18): 1, more preferably (14 to 16): 1, a step of; the zirconia ball-milling beads are preferably prepared from zirconia ball-milling beads with the diameter of 5mm, zirconia ball-milling beads with the diameter of 3mm and zirconia ball-milling beads with the diameter of 1mm according to the mass ratio of (1-2): (2-3): 1. In the present invention, the rotational speed of the ball mill is preferably 300 to 1000rpm, more preferably 500 to 800rpm.
In the present invention, the temperature of the metathesis reaction is preferably 300 to 400 ℃, and the time is preferably 4 to 10 hours, more preferably 5 to 7 hours.
After the metathesis reaction, the invention preferably further comprises cooling to room temperature under deuterium conditions, and then removing the crude sodium borodeuteride under a protective atmosphere. In the present invention, the protective atmosphere preferably includes argon.
After the crude sodium borodeuteride is obtained, the crude sodium borodeuteride is extracted, and the obtained extraction phase is dried to obtain the sodium borodeuteride.
In the present invention, the extracting agent for extraction is preferably an organic amine; the organic amine preferably includes one or more of n-propylamine, n-butylamine, cyclohexylamine, ethylenediamine, triethylamine, and aniline, and further preferably includes one or more of ethylenediamine, cyclohexylamine, and aniline.
In the invention, the mass ratio of the extracted extractant to the sodium borodeuteride crude product is preferably (2-10): 1, more preferably (4 to 7): 1, more preferably (5 to 6): 1.
in the invention, the extraction can dissolve sodium borodeuteride in the crude sodium borodeuteride product into the extractant, and other impurities (such as NaBO 2 MgO, etc.) is precipitated by being insoluble in the extractant, and impurities are removed by subsequent filtration.
After the extraction, the invention preferably further comprises filtering, and the obtained filtrate is an extraction phase.
In the present invention, the filtration is preferably performed under a protective atmosphere, which preferably includes argon. In the present invention, the filtration membrane is preferably a polytetrafluoroethylene membrane, and the pore size of the polytetrafluoroethylene membrane is preferably 0.22. Mu.m.
In the present invention, the drying means is preferably freeze-drying, and the time of the freeze-drying is preferably 12 to 24 hours.
The following is a detailed description of the preparation method of sodium borodeuteride provided by the present invention in connection with examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Calcining 0.421kg of fiber boron magnesium powder (with the particle size of 100 μm) for 4 hours under argon atmosphere at 500 ℃, and then reducing the temperature to 30 ℃ under the argon atmosphere to obtain calcined fiber boron magnesium powder for sealing for later use; 0.174kg of the boron trioxide powder with the grain size of 200-100 meshes is calcined for 3 hours under the argon atmosphere at 400 ℃, and then the temperature is reduced to 30 ℃ under the argon atmosphere, so as to obtain the calcined boron trioxide powder, and the calcined boron trioxide powder is sealed for later use.
The calcined fiber boron magnesium powder (molar quantity of boron element a) 1 Molar amount a of sodium element of 5.5mol 2 0), calcined diboron trioxide powder (molar amount of boron element n: 2.5 mol) was successively charged into a 10L stainless steel high-energy ball milling reactor, followed by continuing to add thereto 2.420kg of sodium deuterated phenolate (molar amount of sodium b: 20.0 mol) and 1.500kg of sodium deuterated (molar amount of deuterium element c: 60.0 mol); wherein (a) 2 +b)：(a 1 +n)＝2.5：1，(a 1 +n)：c＝1：7.5。
Putting 1.044kg of 5mm zirconia ball-milling beads, 1.044kg of 3mm zirconia ball-milling beads and 0.522kg of 1mm zirconia ball-milling beads into a stainless steel high-energy ball-milling reactor, then sealing the reactor, replacing air in the reactor with deuterium gas, starting the ball-milling machine after 4 times of replacement, wherein the ball-milling rotating speed is 600rpm, reacting at 300 ℃ for 7 hours, replacing deuterium gas in the reactor with argon gas after the reaction is finished and the materials in the ball-milling machine are cooled to room temperature, and then taking out the materials in the reactor to obtain 4.472kg of sodium borodeuteride crude product.
Adding 4.472kg of the crude sodium borodeuteride into 15kg of ethylenediamine for extraction, then filtering the crude sodium borodeuteride into a polytetrafluoroethylene membrane with the pore diameter of 0.22 mu m under the argon atmosphere to obtain a filtrate, and freeze-drying the filtrate at the temperature of-20 ℃ for 24 hours by a vacuum freeze dryer to obtain 0.418kg of refined solid sodium borodeuteride product; the yield was 27.8% and the purity was 99.5%, with deuterium abundance in the sample measured using a time-of-flight secondary ion mass spectrometer being greater than 99.0%.
Example 2
Calcining 121.6g of natrium borideum powder (particle diameter of 90 μm) for 4.5h under argon atmosphere at 450 ℃, and then reducing the temperature to 30 ℃ under argon atmosphere to obtain calcined natrium borideum powder for sealing for later use; 52.3g of the boron trioxide powder with the grain size of 200-100 meshes is calcined for 4 hours under the argon atmosphere at 400 ℃, and then the temperature is reduced to 30 ℃ under the argon atmosphere, so as to obtain the calcined boron trioxide powder, and the calcined boron trioxide powder is sealed for later use.
The calcined sodiumdorolysis powder (molar amount of boron element a) 1 Molar amount a of sodium element of 1.5mol 2 0.3 mol) and calcined diboron trioxide powder (molar amount of boron element n: 0.75) were successively charged into a 1L stainless steel high-energy ball milling reactor, followed by continuing to add thereto 246.2g of sodium deuterated amide (molar amount of sodium b: 6.0 mol) and 189.2g of lithium deuteride (molar amount of deuterium element c: 21.1 mol); wherein (a) 2 +b)：(a 1 +n)＝2.8：1，(a 1 +n)：c＝1：9.38。
209.1g of 5mm zirconia ball-milling beads, 209.1g of 3mm zirconia ball-milling beads and 104.5g of 1mm zirconia ball-milling beads are placed into a stainless steel high-energy ball-milling reactor, then the reactor is sealed, the air in the reactor is replaced by deuterium, the ball mill is started after 4 times of replacement, the ball milling rotating speed is 700rpm, the reaction time is 5 hours at 300 ℃, the deuterium in the reactor is replaced by argon after the reaction is finished and the materials in the ball mill are cooled to room temperature, and then the materials in the reactor are taken out, so as to obtain 609.1g of sodium borodeuteride crude product.
Adding 609.1g of crude sodium borodeuteride into 5kg of cyclohexylamine for extraction, then filtering the crude sodium borodeuteride product through a polytetrafluoroethylene membrane with the pore diameter of 0.22 mu m under argon atmosphere to obtain filtrate, and freeze-drying the filtrate at the temperature of minus 20 ℃ for 24 hours through a vacuum freeze dryer to obtain 124.2g of refined solid sodium borodeuteride product; the yield was 65.6% and the purity was 99.5%, with deuterium abundance in the sample measured using a time-of-flight secondary ion mass spectrometer being greater than 99.0%.
Example 3
Calcining 425.7g of natrium borite powder (particle diameter of 90 μm) under argon atmosphere at 450 ℃ for 5h, and then respectively reducing the temperature to 30 ℃ under argon atmosphere to obtain natrium borite powder, calcining and sealing for later use; 78.4g of the boron trioxide powder with the grain size of 200-100 meshes is calcined for 6 hours under the argon atmosphere at 400 ℃, and then the temperature is reduced to 30 ℃ under the argon atmosphere, so as to obtain the calcined boron trioxide powder, and the calcined boron trioxide powder is sealed for later use.
The calcined natrium borite powder (molar quantity of boron element a) obtained above 1 Molar amount of sodium element a of 5.25mol 2 1.05 mol) and calcined diboron trioxide powder (molar amount of boron element n: 3.38 mol) were successively charged into a 10L stainless steel high-energy ball milling reactor, followed by further adding thereto 956.8g of sodium oxide (molar amount of sodium b: 30.88 mol) and 1265.5g of titanium deuteride (molar amount of deuterium element c: 48.78 mol); wherein (a) 2 +b)：(a 1 +n)＝3.7：1，(a 1 +n)：c＝1：5.65。
313.6g of 5mm zirconia ball-milling beads, 392g of 3mm zirconia ball-milling beads and 156.8g of 1mm zirconia ball-milling beads are placed into a stainless steel high-energy ball-milling reactor, then the reactor is sealed, the air in the reactor is replaced by deuterium, the ball mill is started after 4 times of replacement, the ball milling rotating speed is 800rpm, the reaction time is 6 hours at 350 ℃, after the reaction is finished, the deuterium in the reactor is replaced by argon after the ball mill is cooled to room temperature, and then the reactor is taken out, so as to obtain 2933.3g of sodium boron deuteride crude product.
Adding 2933.3g of the crude sodium borodeuteride product into 10kg of ethylenediamine for extraction, then filtering the crude sodium borodeuteride product through a polytetrafluoroethylene membrane with the pore diameter of 0.22 mu m under the argon atmosphere to obtain a filtrate, and freeze-drying the filtrate at the temperature of-20 ℃ for 24 hours through a vacuum freeze dryer to obtain 314.4g of refined solid sodium borodeuteride product; the yield was 10.7% and the purity was 99.5%, with deuterium abundance in the sample measured using a time-of-flight secondary ion mass spectrometer being greater than 99.0%.
Example 4
Respectively 3.84kg of sodium borate calcium stone powder (particle size is 50 μm) is calcined at 700℃under an argon atmosphere for 3 hours, then, the temperature is reduced to 30 ℃ in the argon atmosphere, and the calcined fine ground limestone borate is obtained and sealed for later use; 0.47kg of the boron trioxide powder with the grain size of 200-100 meshes is calcined for 5 hours under the argon atmosphere at 450 ℃, and then the temperature is reduced to 30 ℃ under the argon atmosphere, so as to obtain the calcined boron trioxide powder, and the calcined boron trioxide powder is sealed for later use.
Calcining the obtained sodium calcium borate stone powder (molar quantity of boron element a) 1 Molar amount of sodium element a of 31.5mol 2 31.5 mol) and calcined diboron trioxide powder (molar amount of boron element n: 13.5 mol) were successively charged into a 20L stainless steel high-energy ball milling reactor, followed by continuing to add thereto 9.85kg of sodium deuterated ethoxide (molar amount of sodium: 134.8 mol) and 16.07kg of zirconium deuteride (molar amount of deuterium element: c: 337.5 mol); wherein (a) 2 +b)：(a 1 +n)＝3.7：1，(a 1 +n)：c＝1：7.5。
Placing 1.88kg of 5mm zirconia ball-milling beads, 2.35kg of 3mm zirconia ball-milling beads and 0.94kg of 1mm zirconia ball-milling beads into a stainless steel high-energy ball-milling reactor, then sealing the reactor, replacing air in the reactor with deuterium gas, starting the ball-milling machine after 4 times of replacement, wherein the ball-milling rotating speed is 900rpm, reacting at 350 ℃ for 7 hours, replacing deuterium gas in the reactor with argon gas after the reaction is finished and the materials in the reactor are cooled to room temperature, and then taking out the materials in the reactor to obtain 30.23kg of sodium borodeuteride crude product.
Adding 30.23kg of the crude sodium borodeuteride product into 100kg of aniline for extraction, then filtering the crude sodium borodeuteride product through a polytetrafluoroethylene membrane with the pore diameter of 0.22 mu m under the argon atmosphere to obtain filtrate, and freeze-drying the filtrate at the temperature of minus 20 ℃ for 24 hours through a vacuum freeze dryer to obtain 1.88kg of refined solid sodium borodeuteride product; the yield was 11.7% and the purity was 99.5%, with deuterium abundance in the sample measured using a time-of-flight secondary ion mass spectrometer being greater than 99.0%.
Example 5
Respectively adding 2.19kg of sodium borate calcium stone powder (particle size is 50 μm) is calcined under an argon atmosphere at 750℃for 6 hours, then, the temperature is reduced to 30 ℃ in the argon atmosphere, and the calcined fine ground limestone borate is obtained and sealed for later use; 0.16kg of the boron trioxide powder with the grain size of 200-100 meshes is calcined for 3 hours under the argon atmosphere at the temperature of 650 ℃, and then the temperature is reduced to 30 ℃ under the argon atmosphere, so as to obtain the calcined boron trioxide powder, and the calcined boron trioxide powder is sealed for later use.
2.19kg of calcined fine ground limestone boron powder (molar amount of boron element a) 1 17.97mol, molar weight a of sodium element 2 17.97 mol) and 0.16kg of calcined diboron trioxide powder (the molar amount of boron element n is 6.89 mol) were successively charged into a 15L stainless steel high-energy ball-milling reactor, followed by further adding thereto 2.77kg of deuterated sodium amide (the molar amount of sodium b is 67.56 mol) and 2.10kg of aluminum trideuteride (the molar amount of deuterium element c is 190.91); wherein (a) 2 +b)：(a 1 +n)＝3.44：1，(a 1 +n)：c＝1：7.68。
Placing 0.68kg of 5mm zirconia ball-milling beads, 0.85kg of 3mm zirconia ball-milling beads and 0.34kg of 1mm zirconia ball-milling beads into a stainless steel high-energy ball-milling reactor, then sealing the reactor, replacing air in the reactor with deuterium gas, starting the ball mill after 4 times of replacement, wherein the ball-milling rotating speed is 900rpm, reacting at 400 ℃ for 5 hours, replacing deuterium gas in the reactor with argon gas after the reaction is finished and the materials in the reactor are cooled to room temperature, and then taking out the materials in the reactor to obtain 7.22kg of sodium borodeuteride crude product.
Adding 7.22kg of the crude sodium borodeuteride product into 20kg of aniline for extraction, filtering the obtained product by a polytetrafluoroethylene membrane with the pore diameter of 0.22 mu m under the argon atmosphere to obtain filtrate, and freeze-drying the filtrate at the temperature of minus 20 ℃ for 24 hours by a vacuum freeze dryer to obtain 0.94kg of refined solid sodium borodeuteride product, wherein the yield is 44.7%, the purity is 99.5%, and the deuterium abundance in a sample measured by using a time-of-flight secondary ion mass spectrometer is greater than 99.0%.
Fig. 1 is an XRD spectrum of sodium borodeuteride obtained in example 1, as can be seen from fig. 1: the measured peak positions of the samples correspond to the standard XRD of sodium borodeuteride.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The preparation method of the sodium borodeuteride is characterized by comprising the following steps:
respectively calcining the boron-containing material and the boron trioxide to obtain a calcined boron-containing material and calcined boron trioxide;
mixing the calcined boron-containing material, calcined diboron trioxide, a sodium-containing compound and a metal deuteride, and carrying out double decomposition reaction under the condition of deuterium to obtain a sodium borodeuteride crude product;
extracting the sodium borodeuteride crude product, and drying the obtained extraction phase to obtain the sodium borodeuteride;
the boron-containing material comprises one or more of fibrous boron magnesium powder, natroborolysis powder and boron natralcite powder;
the sodium-containing compound comprises one or more of sodium deuteride sodium phenolate, sodium deuteride amino, sodium oxide and sodium deuteride ethanol;
the metal deuterides include one or more of lithium deuteride, titanium deuteride, sodium deuteride, zirconium deuteride, and aluminum tridentate;
the molar quantity of boron element in the boron-containing material is a1, and the molar quantity of sodium element is a2; the molar quantity of boron element in the diboron trioxide is n; the molar quantity of sodium element in the sodium-containing compound is b; the molar weight of deuterium element in the metal deuteride is c;
a 1 、a 2 n, b and c satisfy the following relationship:
(a 2 +b)：(a 1 +n)＝(2～4)：1；
(a 1 +n)：c＝1：(5～10)；
the temperature of the calcination is independently 350-750 ℃ and the time is independently 3-6 h; the calcination is independently performed under a protective atmosphere;
the double decomposition reaction is carried out under the condition of ball milling; the ball-milling beads are zirconium oxide ball-milling beads, and the mass ratio of the zirconium oxide ball-milling beads to the diboron trioxide is (10-20): 1, the zirconia ball-milling beads are prepared from zirconia ball-milling beads with the diameter of 5mm, zirconia ball-milling beads with the diameter of 3mm and zirconia ball-milling beads with the diameter of 1mm according to the mass ratio of (1-2): (2-3): 1, mixing;
the temperature of the double decomposition reaction is 300-400 ℃ and the time is 4-10 h.
2. The method of claim 1, wherein the extracted extractant is an organic amine; the organic amine comprises one or more of n-propylamine, n-butylamine, cyclohexylamine, ethylenediamine, triethylamine and aniline.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the extracted extractant to the crude sodium borodeuteride is (2-10): 1.
4. the method according to claim 1, wherein the drying is freeze-drying for 12 to 24 hours.
5. The method of claim 1, wherein the particle size of the diboron trioxide is less than 100nm.
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| CN104176749A (en) * | 2014-07-02 | 2014-12-03 | 北京理工大学 | Method for preparing lithium deuteride by using high-temperature direct manner |
| CN105502292A (en) * | 2016-02-03 | 2016-04-20 | 上海化工研究院 | Preparation method for stable isotope reagent sodium borodeuteride |
| CN106477523A (en) * | 2016-09-20 | 2017-03-08 | 华南理工大学 | A kind of method that Room Temperature Solid State ball milling is directly synthesized sodium borohydride |
| CN108545699A (en) * | 2018-04-03 | 2018-09-18 | 华南理工大学 | The method that Room Temperature Solid State ball milling directly synthesizes sodium borohydride |
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| CN106477523A (en) * | 2016-09-20 | 2017-03-08 | 华南理工大学 | A kind of method that Room Temperature Solid State ball milling is directly synthesized sodium borohydride |
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