CN86108142A - The preparation method of sodium borohydride - Google Patents
The preparation method of sodium borohydride Download PDFInfo
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- CN86108142A CN86108142A CN86108142.0A CN86108142A CN86108142A CN 86108142 A CN86108142 A CN 86108142A CN 86108142 A CN86108142 A CN 86108142A CN 86108142 A CN86108142 A CN 86108142A
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- borax
- sodium borohydride
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Abstract
A kind of is raw material with borax, sodium Metal 99.5 and hydrogen, the method of synthetic sodium borohydride in the presence of quartz sand, this law is compared with at present international trimethyl borate method (Schlesiger method), has raw material and is easy to get, technical process is easy, advantages such as convenient post-treatment; Compare with borax method (Bayer method), reaction can be carried out under normal pressure, and temperature of reaction is lower, and operational safety, technology are rationally economical, essentially no three-waste pollution.
Description
The invention belongs to the preparation method of alkali metal borohydride.
Sodium borohydride be nineteen forty-two by people such as Schlesinger synthetic first.Because it has multiple use at aspects such as boron-containing high-energy fuel, open-air hydrogen manufacturing, papermaking and textile industries, make it successively to drop into suitability for industrialized production in states such as Europe, the United States in the latter stage fifties.The raw material of synthetic boron hydrogen sodium mainly contains four big classes:
＜1〉boric acid ester
＜2〉boron oxide and borate
＜3〉halogenide of boron
＜4〉borine and organic boron.
Realize that wherein industrial method mainly is boric acid ester method (also claiming the Schlesinger method) and borax method (also claiming the Bayer method).The boric acid ester method is to generate sodium borohydride: B(OCH with gas phase trimethyl borate and sodium hydride reaction
3)
3+ 4NaH (250 ℃)/() NaBH
4+ 3NaOCH
3Because the heat release of when reaction is more, temperature control is difficulty comparatively, industrial be sodium hydride to be dispersed in the mineral oil (see U.S.Pat 3,002,806 with the trimethyl borate reaction; Ger pat 1,037,428 and (1)).This method has that temperature of reaction is low, technology is easy to serialization, is suitable for scale operation, but also exists technical process long, and by product (methyl alcohol) has shortcomings such as pollute and aftertreatment is more numerous and diverse to environment; The total reaction of borax method can be represented by the formula:
This reaction can make Borax pentahydrate, sodium and quartz sand mix back single step reaction (seeing Brit 962,228), also can make the hydrogenation under 290-310 ℃, a 3-5 hydrogen pressure of Borax pentahydrate and sodium, then with sodium hydride, Borax pentahydrate and the small amount of N aBH of generation
4Mixture and quartz sand reaction under 440 °-460 ℃ and 4 hydrogen pressures (see Brit 962,005), also can adopt the way (6 of other improvement, 7), but the above-mentioned borax method that adopts, all must under higher pressure, could obtain higher transformation efficiency, so having relatively high expectations to equipment performance.
The objective of the invention is to work out a kind of synthetic NaBH
4Perfect method, this method must have that raw material is easy to get, technical process is easy, temperature of reaction is low, convenient post-treatment, three-waste free pollution, characteristics such as can react under normal pressure.
As long as experiment showed, and control granularity, temperature of reaction and the reaction times of Borax pentahydrate, quartz sand well, be to find synthesis technique with These characteristics.
Use the synthetic sodium borohydride of method of the present invention to compare with the method (schlesinger method) of present international trimethyl borate, have raw material and be easy to get, technical process is easy, advantages such as convenient post-treatment; Compare with borax method (Bayer method), its reaction can be carried out under normal pressure, and temperature of reaction is lower, operational safety, and less demanding to equipment performance, three-waste free pollution problem again; The NaBH that uses technology of the present invention to make
4Be the crystal powder of white, purity is more than 97%, and the total recovery of its product (by borax) is greater than 70%.
Embodiment
1. raw-material processing
＜1〉borax must be calcined 4 hours in 500 ℃ retort furnace, could dewater fully.Pulverize on ball mill after dehydration finishes, it is standby to get 140 purpose components.
＜2〉quartz sand (20-40 order) is pulverized on ball mill, it is standby to get 140-200 purpose component.
＜3〉sodium Metal 99.5 is taken out from white oil, inhale the oil stain that goes to the surface,, be cut into 5 * 5mm rapidly with exsiccant petroleum ether twice with paper
2Slice standby.
2.NaBH
4Synthetic and fixed
Take by weighing 30.2 grams (0.15Mol) and cross 140 purpose Borax pentahydrates and 63.9 gram (1.05Mol) 140-200 purpose quartz sands, pour in the reactor rapidly, tighten the logical hydrogen of Fu Gai And, slice sodium 55.2 is restrained (2.4Mol) rapidly by the dog-house input, after tightening dog-house, vacuumize, fill hydrogen, Chou Zhen Kong And fills hydrogen again, repeats aforesaid operations till lighting the tail gas that receives and not having explosion.Under 50mm mercury column hydrogen pressure, make reactant rise to 120 ℃ by room temperature, start Jiao Ban And and be warming up to 300 ℃, be incubated 5-6 minute down at 300 ℃ and be warming up to 360 °-370 ℃ again, insulation can stop to stir cooling in 12 minutes after hydrogen to be inhaled finished, with the product porphyrize, sampling analysis, reaction conversion ratio is that 85-90%(is in sodium Metal 99.5 after the cooling), reaction product promptly obtains the white solid product through Isopropylamine extraction, purity greater than 97%(with activity hydrogen meter).It is as follows that its decides the result:
＜1〉ultimate analysis: B(%) 27.68 H(%) 10.36
B∶H（Mol）＝1∶4.01
＜2〉X ray material phase analysis
It is as shown in table 1 by the d value that spectrogram calculates that solid sodium borohydride is carried out X-ray powder diffraction (Fig. 1) with Japanese D/max-rAX x ray diffractometer x of science:
＜3〉thermal stability determination
Sodium borohydride is DSC in nitrogen atmosphere and vacuum, the result shows, 503 ℃ of decomposition in nitrogen are described consistent with document (8); 420 ℃ of decomposition in a vacuum, slightly higher than literature value (400 ℃).
＜4〉photomicrography
SODIUM BOROHYDRIDE POWDER is throwed Photomicrograph (magnification 200, the exposure time is 8 seconds) under the white oil protection, the results are shown in Figure 2.Find out the prepared NaBH of the present invention from photo
4It is the complete cubic system of external form.
Reference
〔1〕W.H.Schlechter，C.B.Jackzon????and????R.M.Adams
“Boron????Hydrides????and????Related????Compounds”
Callery????Chem.Co.May????1954.
〔2〕F.Schubert????and????k.Lang.
Angew.Chem.72，994（1960）.
〔3〕F.Schubert，K.Lang????and????A.Burger????DBP
1，088，930（1960）。
Claims (3)
1, the method for the synthetic sodium borohydride of the improved borax method of a kind of employing (Bayer method), it is characterized in that it be Borax pentahydrate, quartz sand and sodium Metal 99.5 according to weight ratio be 1: 2.11: 1.82 proportioning once join reactor interior, made NaBH in 12 minutes 360 ° of-370 ℃ of following insulation reaction
4.
2, according to the method for the synthetic sodium borohydride of the improved borax method of the said usefulness of claim 1, the granularity that it is characterized in that Borax pentahydrate is less than 140 orders, and the granularity of quartz sand is the 140-200 order.
3, according to the method for the synthetic sodium borohydride of the improved borax method of the said usefulness of claim 1, the hydrogen pressure when it is characterized in that reacting is the 50mm mercury column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86108142 CN1006697B (en) | 1986-11-28 | 1986-11-28 | Prepn. of sodium borohydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86108142 CN1006697B (en) | 1986-11-28 | 1986-11-28 | Prepn. of sodium borohydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86108142A true CN86108142A (en) | 1988-06-08 |
| CN1006697B CN1006697B (en) | 1990-02-07 |
Family
ID=4803816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86108142 Expired CN1006697B (en) | 1986-11-28 | 1986-11-28 | Prepn. of sodium borohydride |
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| Country | Link |
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| CN (1) | CN1006697B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6524542B2 (en) | 2001-04-12 | 2003-02-25 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| US6670444B2 (en) | 2000-11-08 | 2003-12-30 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| US7019105B2 (en) | 2000-11-08 | 2006-03-28 | Millennium Cell, Inc. | Compositions and processes for synthesizing borohydride compounds |
| CN101891152A (en) * | 2010-07-29 | 2010-11-24 | 浙江大学 | Preparation method of lithium borohydride |
| CN115072663A (en) * | 2022-07-13 | 2022-09-20 | 山东国邦药业有限公司 | Preparation method of lithium borohydride and zinc borohydride |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2502971C (en) * | 2004-04-12 | 2009-10-27 | Rohm And Haas Company | Process for production of a borohydride compound |
-
1986
- 1986-11-28 CN CN 86108142 patent/CN1006697B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6670444B2 (en) | 2000-11-08 | 2003-12-30 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| US7019105B2 (en) | 2000-11-08 | 2006-03-28 | Millennium Cell, Inc. | Compositions and processes for synthesizing borohydride compounds |
| US6524542B2 (en) | 2001-04-12 | 2003-02-25 | Millennium Cell, Inc. | Processes for synthesizing borohydride compounds |
| CN101891152A (en) * | 2010-07-29 | 2010-11-24 | 浙江大学 | Preparation method of lithium borohydride |
| CN101891152B (en) * | 2010-07-29 | 2012-06-06 | 浙江大学 | Preparation method of lithium borohydride |
| CN115072663A (en) * | 2022-07-13 | 2022-09-20 | 山东国邦药业有限公司 | Preparation method of lithium borohydride and zinc borohydride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1006697B (en) | 1990-02-07 |
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