CN1051152A - The synthetic method of sodium aluminum hydride - Google Patents
The synthetic method of sodium aluminum hydride Download PDFInfo
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- CN1051152A CN1051152A CN 89108190 CN89108190A CN1051152A CN 1051152 A CN1051152 A CN 1051152A CN 89108190 CN89108190 CN 89108190 CN 89108190 A CN89108190 A CN 89108190A CN 1051152 A CN1051152 A CN 1051152A
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- sodium
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- nah
- alcl
- naalh
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Abstract
Present patent application provides a kind of method of fully new synthesizing hydrogenated aluminium sodium, at first with the technology that is different from the synthesizing hydrogenated sodium of catalysis under the classical normal temperature and pressure, the sodium hydride that produces is the active high solid of fine dispersive, can generate sodium aluminum hydride than the smooth reaction of carrying out under the normal temperature by metering with the aluminum chloride tetrahydrofuran solution, need not add initiator, equipment is simple, and processing ease is grasped, and the method for safety and save energy consumption is provided for the synthesizing hydrogenated aluminium sodium in laboratory.
Description
The invention belongs to inorganic synthetic chemistry field.
Sodium aluminum hydride NaAlH
4Be Schlesinger and Finholt [H.I.Schlesinger and A.E.Finholt, U.S.Patent.2576311(1951)] in the nineteen fifty-one reported first.
It is the very strong complex metal hydride of a kind of reducing property, its reductibility and LiAlH
4Close.Owing in composition, replace lithium, should be a kind of LiAlH of ratio with sodium
4Use the more inexpensive widely original reagent of going back, but owing to there is certain difficulty on the synthetic method, cause this product still to fail commercialization so far in the international market.
The synthetic method of reporting in the document [U.S.Patent 2576311(1951), Czech, Patent 89103(1959), U.S.Patent 2900-224(1959)] be that aluminum bromide and sodium hydride are reacted in ether type solvent, or make catalyzer with triethyl aluminum, make the reaction of aluminum chloride and sodium hydride, generate NaAlH
4
The sodium-chlor crystallite that generates during the point of the difficulty of this class reaction is to react is deposited on the sodium hydride particle, has blocked proceeding of reaction, and speed of response slows down gradually so that last blocking-up.The sodium-chlor of under agitation separating out in addition forms gelatinous precipitate in solvent, make product be difficult to separate.
The objective of the invention is to find out the synthetic NaAlH of a kind of simple and practical method fork-like farm tool used in ancient China
4
The present invention at first utilizes the organometallic catalytic reaction to change the synthetic method of sodium hydride, the hydrogenation of sodium Metal 99.5 can be carried out under normal temperature and pressure conditions, saved energy consumption, and generate the sodium hydride of active very high minuteness particle, eccysis catalyzer then, in tetrahydrofuran (THF), make the reaction of sodium hydride and aluminum chloride tetrahydrofuran solution again, synthesizing hydrogenated aluminium sodium.Building-up reactions do not need initiator at normal temperatures quick and stable carry out, reaction formula is as follows:
(1) the normal temperature and pressure catalysis hydrogenation of sodium Metal 99.5:
Catalyzer=naphthalene+TiCl
4The THF=tetrahydrofuran (THF)
(2) complex reaction of sodium hydride and aluminum chloride:
The characteristics and the effect of this synthetic method are:
(1) sodium hydride is synthetic greatly different with classical way, and catalysis at normal temperatures and pressures is synthetic, and except having saved the energy, the products therefrom sodium hydride has very high chemically reactive.
(2) second go on foot complex reactions because of NaH activity height and fine dispersion, and reaction does not need initiator, directly direct at normal temperatures the and AlCl by the metering ratio
3The reaction times has been shortened in rapid reaction.
(3) appointed condition is simple, operates simple and easyly, and raw material is easy to get, and is dangerous little.Productive rate counts 65% according to sodium, and purity can reach 70%, can reach 95% through recrystallization purity in THF.
The synthetic test example
The catalysis of [example 1] sodium hydride is synthetic
In argon atmospher, with 0.2 mole of chopping sodium Metal 99.5,0.02 mole of naphthalene and 120 milliliters of tetrahydrofuran (THF)s are put into exsiccant reaction garden flask, add 0.004 mole of titanium tetrachloride, under agitation feed hydrogen then, with hydrogen flowmeter monitoring hydrogen consumption.When air inlet with go out to be reaction end when airshed equates.Cool off the reaction mixture centrifugal settling that makes short of money, supernatant liquid is received in suction, uses an amount of tetrahydrofuran (THF) washed product eccysis for several times catalyzer then, at last product is drained in a vacuum the sampling and measuring active hydrogen in the moisture eliminator.Product purity is higher than 90%.In the sodium productive rate is quantitative basically.The sodium hydride activity that this method makes is very high, and meeting spontaneous combustion in air is so operation should be carried out in inert atmosphere.
The building-up reactions of [example 2] sodium aluminum hydride
Calculate according to above-mentioned sodium hydride purity, take by weighing stoichiometric aluminum trichloride (anhydrous), be dissolved among an amount of THF.Under nitrogen atmosphere, the sodium hydride of metering is transferred in the three neck garden flasks, added an amount of THF and form suspension, load onto reflux condensing tube then, dropping funnel and agitator.Under agitation by dropping funnel with AlCl
3(THF) dropwise join in the THF suspension of NaH.Temperature of reaction maintains about 35 ℃.Reaction promptly steadily and is apace carried out.After dropwising, continue to stir 6-7 hour, left standstill then 48 hours.Aspirate out supernatant liquid, add the dry toluene be slightly less than the clear liquid volume, be not higher than at oil bath temperature under 80 ℃ the condition and steam tetrahydrofuran (THF), promptly get the NaAlH of white crystals shape
4, purity is 70%, is 65% according to NaH meter productive rate, product can reach 95% through a THF recrystallization purity.
The X-ray diffraction spectrogram of products obtained therefrom is seen Fig. 1, and is consistent with ASTM card standard spectrogram.
Claims (3)
1, a kind ofly prepares NaH with sodium Metal 99.5 and hydrogen reaction, the latter and AlCl
3Prepared in reaction NaAlH
4Method, be with naphthalene and TiCl when it is characterized in that preparing NaH
4Make catalyzer, synthetic under normal temperature in the tetrahydrofuran (THF) medium, and NaH and AlCl
3Reaction do not need initiator, rapid reaction at normal temperatures and make NaAlH
4
2, prepare NaH with sodium Metal 99.5 and hydrogen reaction, the latter and AlCl according to claim 1 is said
3Prepared in reaction NaAlH
4Method, when it is characterized in that preparing NaH, Na, naphthalene, TiCl
4Mol ratio be 1: 0.1: 0.02, the consumption of tetrahydrofuran (THF) adds 600 milliliters of calculating by every mole metal sodium.
3, prepare NaH with sodium Metal 99.5 and hydrogen reaction, the latter and AlCl according to claim 1 is said
3Prepared in reaction NaAlH
4Method, it is characterized in that NaH and AlCl
3During reaction, NaH and AlCl
3Mol ratio be 4: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108190 CN1022098C (en) | 1989-10-25 | 1989-10-25 | Process for synthesis of aluminium sodium hydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108190 CN1022098C (en) | 1989-10-25 | 1989-10-25 | Process for synthesis of aluminium sodium hydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1051152A true CN1051152A (en) | 1991-05-08 |
| CN1022098C CN1022098C (en) | 1993-09-15 |
Family
ID=4857480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108190 Expired - Fee Related CN1022098C (en) | 1989-10-25 | 1989-10-25 | Process for synthesis of aluminium sodium hydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1022098C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304276C (en) * | 2003-12-04 | 2007-03-14 | 复旦大学 | Aluminum-containing nano complex hydrogen storage material and its preparation method |
| CN101531338B (en) * | 2009-03-13 | 2010-12-01 | 六九硅业有限公司 | Method for preparing sodium aluminum hydride |
| US8197449B2 (en) | 2005-05-10 | 2012-06-12 | Novo Nordisk A/S | Injection device comprising an optical sensor |
| CN104445209A (en) * | 2014-11-28 | 2015-03-25 | 嵩县中科孵化器有限公司 | Preparation method of silane |
| US9950117B2 (en) | 2009-02-13 | 2018-04-24 | Novo Nordisk A/S | Medical device and cartridge |
| CN114437123A (en) * | 2022-02-23 | 2022-05-06 | 沧州临港星辰化工有限公司 | Preparation method of bis (2-methoxyethoxy) aluminum sodium dihydrogen toluene solution |
-
1989
- 1989-10-25 CN CN 89108190 patent/CN1022098C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304276C (en) * | 2003-12-04 | 2007-03-14 | 复旦大学 | Aluminum-containing nano complex hydrogen storage material and its preparation method |
| US8197449B2 (en) | 2005-05-10 | 2012-06-12 | Novo Nordisk A/S | Injection device comprising an optical sensor |
| US8771238B2 (en) | 2005-05-10 | 2014-07-08 | Novo Nordisk A/S | Injection device comprising an optical sensor |
| US9522238B2 (en) | 2005-05-10 | 2016-12-20 | Novo Nordisk A/S | Injection device comprising an optical sensor |
| US9950117B2 (en) | 2009-02-13 | 2018-04-24 | Novo Nordisk A/S | Medical device and cartridge |
| CN101531338B (en) * | 2009-03-13 | 2010-12-01 | 六九硅业有限公司 | Method for preparing sodium aluminum hydride |
| CN104445209A (en) * | 2014-11-28 | 2015-03-25 | 嵩县中科孵化器有限公司 | Preparation method of silane |
| CN114437123A (en) * | 2022-02-23 | 2022-05-06 | 沧州临港星辰化工有限公司 | Preparation method of bis (2-methoxyethoxy) aluminum sodium dihydrogen toluene solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1022098C (en) | 1993-09-15 |
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