CN101269793A - Method for preparing sodium borohydride - Google Patents
Method for preparing sodium borohydride Download PDFInfo
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- CN101269793A CN101269793A CNA2008100369222A CN200810036922A CN101269793A CN 101269793 A CN101269793 A CN 101269793A CN A2008100369222 A CNA2008100369222 A CN A2008100369222A CN 200810036922 A CN200810036922 A CN 200810036922A CN 101269793 A CN101269793 A CN 101269793A
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Abstract
The invention belongs to the technical field of compound preparation, in particular relates to a preparation method of sodium borohydride. The invention is different from the traditional gas-solid heterogeneous reaction, and carries out solid-state reaction by a metal hydride and a boron-containing compound, and then the sodium borohydride is prepared. The reaction in the invention is carried out completely at the inner part of solid-state materials, so the sodium borohydride can be obtained under lower hydrogen pressure even in an atmosphere of inert gases, thus, high-pressure hydrogen avoids to be used and the requirement to equipment is reduced. The preparation method has the advantages of simple technical process and easy realization of scale production.
Description
Technical field
The invention belongs to the compound technical field, be specifically related to a kind of method for preparing sodium borohydride, more particularly, the present invention relates to a kind ofly carry out the method that solid state reaction prepares sodium borohydride by metal hydride and boron-containing compound.
Background technology
Sodium borohydride has strong reducing property, extensive application aspect organic and inorganic chemistry.It can selective reduction aldehyde, the particular functional group on the ketone, acyl chlorides, and in the aqueous solution, sodium borohydride can reduce Fe
3+, Co
2+, Ni
2+, HSO
-3, IO
-3Plasma.On industrial production, sodium borohydride is widely used in pharmacy, Minute Organic Synthesis, pulp bleaching, Industrial Wastewater Treatment, also can be used as the raw material of preparation boron-containing compound.Owing to have high hydrogen content, sodium borohydride also is subjected to very big attention as the research of hydrogen storage material in recent years.
The method of industrial production sodium borohydride mainly contains two kinds at present: Schlesinger method and Bayer method.The former is a raw material with the trimethyl borate, reacts in mineral oil solution, and cost of material is higher, complex procedures.The latter is raw material with the borax, and borax overwhelming majority in reaction process changes sodium metaborate into, thereby the effective rate of utilization of borax only has about 10%.
It is the synthetic sodium borohydride of raw material that the patent report sodium metaborate is arranged, and its reaction is based on the gas-solid out-phase reaction of sodium Metal 99.5 and hydrogen and sodium metaborate.
Be raw material with metal hydride and sodium metaborate in the research paper of publishing both at home and abroad, reaction all need be carried out under the high pressure hydrogen more than the 2MPa, reaction be based on gas-solid out-phase reaction principle, thereby reaction process is higher to equipment requirements, has improved production cost.
Summary of the invention
The object of the invention is to provide the method for preparing sodium borohydride that a kind of technology is simple, cost is low.
The preparation method of sodium borohydride provided by the invention, concrete steps are as follows:
(1) raw material mixes: metal hydride, boron-containing compound are crushed to the 50-50000 order, mix.
(2) briquetting: the reactant that mixes in the step (1) is pressed into closely knit lumpy material with 0.01-1000 ton pressure.
(3) solid state sintering: the briquetting in the step (2) is heated up, under 70-1000 ℃ of temperature, calcined 5 minutes-24 hours.Reaction atmosphere is nitrogen, hydrogen, argon gas, nitrogen and hydrogen mixture or argon-hydrogen gas mixture, and reaction atmosphere pressure is 0.001-2MPa.
In sodium borohydride preparation method of the present invention, step (1) relates to the pre-treatment of raw material.In the used raw material of this step, metal hydride is specially a kind of in sodium hydride, potassium hydride KH, magnesium hydride, hydrolith, lithium hydride, aluminum hydride, titanium hydride and the hydrogen-storage alloy etc. or multiple mixture.Preferred sodium hydride or hydrolith, more preferably sodium hydride.If contain mineral oil, can remove oil purification.Boron-containing compound can be sodium metaborate, borax, Na
2B
3O
5, NaB
3O
5, Na
2B
4O
5, boron oxide, boron magnesium ore deposit, halogenation boron or borophosphoric acid etc., preferred borax or sodium metaborate, more preferably sodium metaborate.Material should dewater before processing, pulverize then, grinding particle size between the 50-50000 order, preferred 300-5000 order.Can add additive in the step (1) also can be without additive, and additive can be selected SiO for use
2, TiO
2, Na
2O or CaO etc., preferred SiO
2, the preferred 100-200 order of its granular size.Can use catalyzer, the simple substance or the compound of the preferred titanium of catalyzer, iron, nickel, cobalt, aluminium or rare earth element also can not selected catalyzer for use, more preferably do not use catalyzer.The material ratio that reactant ratio is determined according to chemical equation, or wherein a certain component excessive all can, the preferred material ratio of determining according to chemical equation.
In sodium borohydride preparation method of the present invention, step (2) relates to reactant and is pressed into block.Particularly, be to carry out briquetting after reactant is mixed, material bears pressure between the 0.01-1000 ton, preferred 1-300 ton.Can select in the briquetting process to carry out gas shield, also can not carry out gas shield, the preferred nitrogen protection with nitrogen or argon gas or hydrogen.Can vacuumize material in the briquetting process, also can not vacuumize, preferred vacuum pumping is to improve the briquetting effect.In the operation of rolling, can adopt once shaped, also can adopt to grind and then rolling repeatedly forming method after rolling, also can adopt the rolling 1-200 purpose fritter etc. that is broken into then, preferred once shaped.
In sodium borohydride preparation method of the present invention, step (3) relates to the material sintering in the step (2).Temperature of reaction is 70-1000 ℃, preferred 300-600 ℃, and more preferably 350-550 ℃.Reaction atmosphere adopts nitrogen, argon gas, argon-hydrogen gas mixture or hydrogen, preferred nitrogen and hydrogen, more preferably hydrogen; Reaction atmosphere pressure is 0.001-2MPa, preferred 0.1-0.5MPa.Also can react in the vacuum.Calcination time is 5 minutes-24 hours, preferred 1-12h.Heat-up rate is selected 1 ℃/min-60 ℃/min, preferred 10-30 ℃/min.
Term among the present invention " utilizes the briquetting method, based on the solid state reaction principle ", is different from the out-phase reaction of pressed powder and inter gas.The characteristics of out-phase reaction are to utilize hydrogen as hydrogen source, and gaseous molecular and solid particulate react, and generate sodium borohydride; Characteristics of the present invention are; utilize exterior mechanical pressure that roll compacting is become block; thereby the reactant particle is closely linked; wherein metal hydride is as hydrogen source; protium spreads from metal hydride and the boride reaction; do not need hydrogen as reactant in the reaction process, hydrogen mainly is as protection gas, can replace it with inactive gass such as nitrogen.Size, the shape of block are not limit, and for example, the block of roll forming can be ground into small-particle again, and however, small-particle is still the block of rolling mistake, and this situation also belongs to protection domain of the present invention.
Be not bound by any theory although do not wish, but the contriver thinks in the inventive method owing to used outside mechanical pressure, thereby make reactant particle tight agglomeration together, reduced the diffusion length of bioactive molecule in the solid state reaction, thereby made preparation process smooth.
Prepare sodium borohydride by the inventive method, reaction is carried out fully.Thereby can in common atmosphere sintering furnace, prepare sodium borohydride, avoided the strict demand of high pressure hydrogen, and technological process be simple, productive rate height, easy realization of large-scale production equipment.
Description of drawings
Fig. 1 is that gained is calcined the back without the reaction product XRD spectra of purifying in the embodiment of the invention 2
Fig. 2 is that gained is calcined the back without the reaction product infrared spectrum of purifying in the embodiment of the invention 2
Fig. 3 is the sodium borohydride XRD spectra after purifying in the embodiment of the invention 2
Fig. 4 is the sodium borohydride infrared spectrum after purifying in the embodiment of the invention 2
Fig. 5 is that gained is calcined the back without the reaction product XRD spectra of purifying among the embodiment 5.
Embodiment
The present invention below will be described in more detail by reference example, but protection scope of the present invention is not limited to these embodiment.
Embodiment 1
(the gloomy Hao in Shanghai Fine Chemical Co., Ltd) removes mineral oil with the technical grade sodium hydride, and it is stand-by to take by weighing 9.6g under nitrogen protection; (traditional Chinese medicines group) dewaters with sodium metaborate, is crushed to the 100-200 order, and it is stand-by to take by weighing 6.58g; (traditional Chinese medicines group) is crushed to the 100-200 order with silicon-dioxide, takes by weighing 12g.Then with the reactant of above-mentioned weighing mechanically mixing 2 hours under nitrogen protection.Under nitrogen protection, said mixture is rolled into piece with 20MPa pressure.Under the 0.1atm hydrogen shield, be warming up to 510 ℃ then, calcined 8 hours, cool to room temperature with the furnace with 10 ℃ of/minute speed.Reaction product is pulverized, added the 150ml Isopropylamine as extraction agent, extract 2h with soxhlet's extractor, then the Isopropylamine distillation is reclaimed, obtain sodium borohydride 2.97g, productive rate is 78.6% of a theoretical value.
Embodiment 2
(the gloomy Hao in Shanghai Fine Chemical Co., Ltd) removes mineral oil with the technical grade sodium hydride, and it is stand-by to take by weighing 12g under nitrogen protection; (traditional Chinese medicines group) dewaters with sodium metaborate, is crushed to the 100-200 order, and it is stand-by to take by weighing 6.58g; (traditional Chinese medicines group) is crushed to the 100-200 order with silicon-dioxide, takes by weighing 12g.Then with the reactant of above-mentioned weighing mechanically mixing 2 hours under nitrogen protection.Under nitrogen protection, said mixture is rolled into piece with 20MPa pressure.Under the protection of normal pressure high pure nitrogen, be warming up to 500 ℃ then, calcined 8 hours, cool to room temperature with the furnace with 5 ℃ of/minute speed.Reaction product is pulverized, added the 150ml Isopropylamine as extraction agent, extract 2h with soxhlet's extractor, then the Isopropylamine distillation is reclaimed, obtain sodium borohydride 2.876g, productive rate is 76.1% of a theoretical value.
Embodiment 3
(the gloomy Hao in Shanghai Fine Chemical Co., Ltd) removes mineral oil with the technical grade sodium hydride, and it is stand-by to take by weighing 9.6g under nitrogen protection; (traditional Chinese medicines group) dewaters with sodium metaborate, is crushed to the 100-200 order, and it is stand-by to take by weighing 6.58g; (traditional Chinese medicines group) is crushed to the 100-200 order with silicon-dioxide, takes by weighing 12g.Then with the reactant of above-mentioned weighing mechanically mixing 2 hours under nitrogen protection.Under nitrogen protection, with 20MPa pressure said mixture is rolled into piece, once more briquetting is crushed to the 50-100 order.Under the 2atm hydrogen shield, be warming up to 480 ℃ then, calcined 6 hours, cool to room temperature with the furnace with 10 ℃ of/minute speed.Reaction product is pulverized, added the 150ml Isopropylamine as extraction agent, extract 2h with soxhlet's extractor, then the Isopropylamine distillation is reclaimed, obtain sodium borohydride 3.13g, productive rate is 82.8% of a theoretical value.
Embodiment 4
(the gloomy Hao in Shanghai Fine Chemical Co., Ltd) removes mineral oil with the technical grade sodium hydride, and it is stand-by to take by weighing 9.6g under nitrogen protection; (traditional Chinese medicines group) dewaters with sodium metaborate, is crushed to the 100-200 order, and it is stand-by to take by weighing 6.58g; (traditional Chinese medicines group) is crushed to the 100-200 order with silicon-dioxide, takes by weighing 12g.Then with the reactant of above-mentioned weighing mechanically mixing 2 hours under nitrogen protection.Under nitrogen protection, with 20MPa pressure said mixture is rolled into piece, once more briquetting is crushed to the 200-300 order, and then said mixture is rolled into piece with 20MPa pressure.Above-mentioned block reaction mixture is warming up to 500 ℃ with 5 ℃ of/minute speed under the 0.1atm hydrogen shield, calcined 15 hours, cool to room temperature with the furnace.Reaction product is pulverized, added the 150ml Isopropylamine as extraction agent, extract 2h with soxhlet's extractor, then the Isopropylamine distillation is reclaimed, obtain sodium borohydride 3.11g, productive rate is 82.3% of a theoretical value.
Embodiment 5
(the gloomy Hao in Shanghai Fine Chemical Co., Ltd) is crushed to the 100-200 order with the technical grade hydrolith, and it is stand-by to take by weighing 8.4g under nitrogen protection; (traditional Chinese medicines group) dewaters with sodium metaborate, is crushed to the 100-200 order, and it is stand-by to take by weighing 6.58g.Then with the reactant of above-mentioned weighing mechanically mixing 2 hours under nitrogen protection.Under nitrogen protection, said mixture is rolled into piece with 20MPa pressure.Under the protection of normal pressure high pure nitrogen, be warming up to 600 ℃ then, calcined 10 hours, cool to room temperature with the furnace with 5 ℃ of/minute speed.Reaction product is pulverized, added the 150ml Isopropylamine as extraction agent, extract 2h with soxhlet's extractor, then the Isopropylamine distillation is reclaimed, obtain sodium borohydride 2.74g, productive rate is 72.6% of a theoretical value.
Claims (5)
1. the preparation method of a sodium borohydride is characterized in that concrete steps are as follows:
(1) raw material mixes: metal hydride, boron-containing compound are crushed to the 50-50000 order, mix then;
(2) briquetting: the reactant that mixes in the step (1) is pressed into closely knit lumpy material with 0.01-1000 ton pressure;
(3) solid state sintering: the briquetting in the step (2) is heated up, under 70-1000 ℃ of temperature, calcined 5 minutes-24 hours; Reaction atmosphere is nitrogen, hydrogen, argon gas, nitrogen-hydrogen gas mixture or argon-hydrogen gas mixture, perhaps is vacuum, and reaction pressure is 0.001-2MPa;
Wherein:
Used metal hydride is one or more in sodium hydride, potassium hydride KH, hydrolith, lithium hydride, titanium hydride, aluminum hydride or the alloy hydrogen storage material in the step (1), and raw material is for containing mineral oil or being pure raw material;
Used boron-containing compound is sodium metaborate, borax, Na in the step (1)
2B
3O
5, NaB
3O
5, Na
2B
4O
5, in the boron oxide, boron magnesium ore deposit, halogenation boron, borophosphoric acid one or more.
2. preparation method according to claim 1 is characterized in that also adding additive in the step (1), and additive is selected SiO for use
2, TiO
2, Na
2Among O or the CaO one or more.
3. preparation method according to claim 1 and 2 is characterized in that also using catalyzer in the step (1), and catalyzer is selected the simple substance or the compound of titanium, iron, nickel, cobalt, aluminium or rare earth element for use.
4. preparation method according to claim 1 is characterized in that in the step (3) that heat-up rate is 1 ℃/min-60 ℃/min.
5, preparation method according to claim 1 is characterized in that calcining temperature is 300-600 ℃ in the step (3), and calcination time is 1-12 hour.
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|---|---|---|---|
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| CN101269793B CN101269793B (en) | 2010-12-29 |
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Cited By (9)
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|---|---|---|---|---|
| WO2015190403A1 (en) * | 2014-06-11 | 2015-12-17 | 吉崎 敦浩 | Method and device for producing sodium borohydride |
| JP5839337B1 (en) * | 2014-06-11 | 2016-01-06 | 吉崎 敦浩 | Method and apparatus for producing sodium borohydride |
| 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 |
| CN108455530A (en) * | 2018-04-04 | 2018-08-28 | 华南理工大学 | A kind of method that Room Temperature Solid State ball milling directly synthesizes sodium borohydride |
| WO2019174245A1 (en) * | 2018-03-14 | 2019-09-19 | 华南理工大学 | Method for preparing lithium borohydride by means of room temperature solid phase ball milling |
| CN110862070A (en) * | 2018-08-28 | 2020-03-06 | 宁夏佰斯特医药化工有限公司 | Novel process for producing potassium borohydride |
| CN111137861A (en) * | 2019-12-31 | 2020-05-12 | 宁夏佰斯特医药化工有限公司 | Preparation process of sodium borohydride |
| CN116374956A (en) * | 2023-04-23 | 2023-07-04 | 华南理工大学 | Preparation method of magnesium borohydride |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1018726B (en) * | 1988-06-11 | 1992-10-21 | 南开大学 | Dry state preparation of sodium borohydride from boron phosphate |
| US6586563B1 (en) * | 2001-12-18 | 2003-07-01 | Millennium Cell, Inc. | Processes for synthesizing alkali metal borohydride compounds |
| TWI265146B (en) * | 2004-10-08 | 2006-11-01 | Rohm & Haas | Direct elemental synthesis of sodium borohydride |
| US7381390B2 (en) * | 2005-12-19 | 2008-06-03 | General Electric Company | Method for manufacturing magnesium borohydride |
| CN101074092A (en) * | 2006-05-19 | 2007-11-21 | 罗门哈斯公司 | Preparation of borohydride salts |
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2008
- 2008-04-30 CN CN2008100369222A patent/CN101269793B/en not_active Expired - Fee Related
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| CN106414314A (en) * | 2014-06-11 | 2017-02-15 | 株式会社氢燃料能源系统 | Method and device for producing sodium borohydride |
| AU2015272643B2 (en) * | 2014-06-11 | 2017-03-02 | Hydric Power Systems Co., Ltd. | Method and apparatus for producing 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 |
| US11420870B2 (en) | 2016-09-20 | 2022-08-23 | South China University Of Technology | Method for directly synthesizing sodium borohydride by solid-state ball milling at room temperature |
| CN106477523B (en) * | 2016-09-20 | 2019-05-14 | 华南理工大学 | A kind of method that Room Temperature Solid State ball milling directly synthesizes sodium borohydride |
| WO2019174245A1 (en) * | 2018-03-14 | 2019-09-19 | 华南理工大学 | Method for preparing lithium borohydride by means of room temperature solid phase ball milling |
| US11807540B2 (en) | 2018-03-14 | 2023-11-07 | South China University Of Technology | Method for preparing lithium borohydride by means of solid-phase ball milling at room temperature |
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| CN111137861A (en) * | 2019-12-31 | 2020-05-12 | 宁夏佰斯特医药化工有限公司 | Preparation process of sodium borohydride |
| CN116374956A (en) * | 2023-04-23 | 2023-07-04 | 华南理工大学 | Preparation method of magnesium borohydride |
| CN116374956B (en) * | 2023-04-23 | 2024-04-16 | 华南理工大学 | Preparation method of magnesium borohydride |
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