CN1011218B - Synthesis of lithium aluminum hydride - Google Patents
Synthesis of lithium aluminum hydrideInfo
- Publication number
- CN1011218B CN1011218B CN 87101196 CN87101196A CN1011218B CN 1011218 B CN1011218 B CN 1011218B CN 87101196 CN87101196 CN 87101196 CN 87101196 A CN87101196 A CN 87101196A CN 1011218 B CN1011218 B CN 1011218B
- Authority
- CN
- China
- Prior art keywords
- lithium
- hydride
- aluminum hydride
- reaction
- lithium aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
- C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention belongs to a synthetic method for an inorganic reagent (lithium aluminum hydride). At present, in foreign countries, lithium metal is used as a raw material, hydrogenation is carried out at high temperature of 680 DGE C to 720 DGE C or high pressure of 340 atm for preparing lithium hydride, and lithium aluminum hydride is prepared through the reaction of lithium hydride and AlCl3. The method has the disadvantages of large energy consumption in production, high requirement for equipment and potential danger. A main raw material used by the present invention is identical to that of the method, but reaction is carried out under the action of a solvent and a catalyst, and the whole reaction can be carried out at normal temperature and pressure.
Description
The invention belongs to the synthetic method of inorganic reagent.
Lithium aluminum hydride (LiAlH
4) be Finholt, Bond and Schlesinger are in nineteen forty-seven synthetic ([1] U.S.2,576,311) first, it is a kind of extremely strong reductive agent [2 that all organic palaces can roll into a ball that almost can reduce, 3,4], also be the propelling agent of rocket and the additive [U.S.3 of high energy fuels, 830,057], but, make it on producing, using, be restricted because its production cost height, energy consumption reach problems such as operational safety greatly.Therefore, explore new synthetic LiAlH
4Method be an important problem.
Produce LiAlH at present in the world
4Still continuing to use Schlesinger method [4,5], promptly is raw material with the metallic lithium, the following and hydrogen reaction generation lithium hydride at high temperature (680 °-720 ℃), the latter and anhydrous AlCl
3In ether solvent, react and the preparation lithium aluminum hydride.This method needs high temperature, and power consumption is big and exist potential danger; Thereafter, people such as Ashby have carried out the work (French Patent 1,235,680 and [6], [7]) of " by the direct synthesizing hydrogenated aluminium lithium of simple substance ", though this method decreases (using 140 ℃) hydrogenation temperature, need to carry out hydrogenation with high pressure (340atm); Shen Panwen, open fair people such as assorted and delivered and be entitled as " research of lithium aluminum hydride novel synthesis " [8], by product (lithium chloride) in the recycle Schlesinger method has been proposed as the problem of the raw material of synthesizing hydrogenated aluminium lithium, this method has reduced cost, but the reaction of preparation lithium hydride still needs to react under nitrogen atmosphere and under 500 °～600 ℃ the high temperature.
In order to address the above problem, we use metallic lithium and hydrogen to make main raw material when synthesizing hydrogenated lithium, (wherein I can be naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2 to make catalyzer with (I+II), 7-dimethylnaphthalene, 2,3-dimethylnaphthalene, 1,6-dimethylnaphthalene, biphenyl, terphenyl, anthracene; II can be titanium tetrachloride or vanadium tetrachloride), its weight ratio is an I: II: lithium=32: 0.77: 3.5, use tetrahydrofuran (THF) to make solvent, synthesizing hydrogenated lithium under normal temperature (27 °～28 ℃) normal pressure, the latter in ether, benzene or toluene solution with anhydrous AlCl
3Prepared in reaction LiAlH
4This law also is applicable to alkali-metal complex hydride (LiAlH such as synthetic lithium, sodium, potassium
4, NaAlH
4, KAlH
4).
This law can be carried out reaction at normal temperatures and pressures, has reduced energy consumption, has simplified production unit, has eliminated the Hazard Factor in the production process, for the scale operation lithium aluminum hydride provides a kind of safe and reliable method.
Example 1
In reaction flask, add 3.5 gram lithiums, 32 gram naphthalene, 0.45ml titanium tetrachloride and 180ml tetrahydrofuran (THF)s, under nitrogen atmosphere, react, stop to be reaction end, use ether washing reaction product (lithium hydride) standby then until inhaling hydrogen.Other takes by weighing the anhydrous AlCl that equivalents is a lithium hydride 4/5
3With being added drop-wise to behind the ether dissolution in lithium hydride-ether mixture, 27 °～28 ℃ following stirring reactions 3 hours, cooling was left standstill and supernatant liquid is distilled, and constantly replenished benzene or toluene, make in the matrass liquid measure keep constant, after ether has steamed substantially, steam residual solvent, obtain lithium aluminum hydride, purity is that 98.1%(measures with active hydrogen), productive rate is that 89.0%(is with AlCl
3Calculate).
Example 2
Make catalyzer with 1-methylnaphthalene-vanadium tetrachloride, all the other are operated with example 1, gained LiAlH
4Purity be 97.8%, productive rate is 89.1%.
Example 3
Make catalyzer with 1-methylnaphthalene-titanium tetrachloride, all the other are operated with example 1, and product purity is 98.2%, and productive rate is 89.3%.
Example 4
Use 1,6-dimethylnaphthalene and titanium tetrachloride are made catalyzer, and all the other are operated with example 1, and product purity is 97.7%, and productive rate is 88.9%.
Example 5
Make catalyzer with 2-methylnaphthalene-titanium tetrachloride, all the other are operated with example 1, and product purity is 98.5%, and productive rate is 89.4%.
Example 6
With 2,3-dimethylnaphthalene-titanium tetrachloride is made catalyzer, and all the other are operated with example 1, and product purity is 97.3%, and productive rate is 88.7%.
Example 7
With 2,7-dimethylnaphthalene-titanium tetrachloride is made catalyzer, and all the other are operated with example 1, and product purity is 97.7%, and productive rate is 89.1%.
Example 8
Make catalyzer with biphenyl and titanium tetrachloride, all the other are operated with example 1, and product purity is 97.1%, and productive rate is 87.1%.
Example 9
Make catalyzer with terphenyl and titanium tetrachloride, all the other are operated with example 1, and product purity is 97.5%, and productive rate is 87.3%.
Example 10
Make catalyzer with anthracene-titanium tetrachloride, all the other are operated with example 1, and product purity is 97.6%, and productive rate is 87.0%.
Reference
1.Finholt，A.E.Bond，A.C and Schlesinger，H.I.J.Am.Chem.Soc.69，1199（1947）.
2.Hurd，D.D.T.An Introduction to Chemistry of hydrides 149，John and Sons，Inc.New York（1952）.
3.Brin H.C.and Kighamurthy，S.Tctrahydron 35，567（1979）.
4.Stinson，S.C.Chemical and Enginerring News 58，44，18～22（1980）.
5.Kirk-Othmer，Encydovedia of Chemical Technology，11，200.
6.Ashby E.C.Chem.Ind.（London）208（1962）.
7.Ashby E.C.Brendel，G.J and Redman，H.E.Inorg.Chem.2，499（1963）.
8. SCI Vol.3 No.2,169-172(1982).
Claims (1)
1, a kind of by metallic lithium and Preparation of Hydrogen lithium hydride, the latter and anhydrous chlorides of rase reactive aluminum and prepare the method for lithium aluminum hydride, when it is characterized in that with metallic lithium and Preparation of Hydrogen lithium hydride, (I can be naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1 as catalyzer to be to use (I+II), 6 dimethylnaphthalenes, 2,7-dimethylnaphthalene, 2,3-dimethylnaphthalene, biphenyl, terphenyl, anthracene; II can be titanium tetrachloride or vanadium tetrachloride), its weight ratio is an I: II: lithium=32: 0.77: 3.5, and use tetrahydrofuran (THF) to make solvent, synthesizing hydrogenated lithium under normal temperature (27 °～28 ℃) normal pressure then, the latter in ether, benzene or toluene solution with anhydrous AlCl
3Prepared in reaction LiAlH
4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101196 CN1011218B (en) | 1987-12-23 | 1987-12-23 | Synthesis of lithium aluminum hydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101196 CN1011218B (en) | 1987-12-23 | 1987-12-23 | Synthesis of lithium aluminum hydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033610A CN1033610A (en) | 1989-07-05 |
| CN1011218B true CN1011218B (en) | 1991-01-16 |
Family
ID=4813242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87101196 Expired CN1011218B (en) | 1987-12-23 | 1987-12-23 | Synthesis of lithium aluminum hydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011218B (en) |
Families Citing this family (5)
| 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 |
| CN106410210B (en) * | 2016-10-31 | 2019-08-09 | 复旦大学 | A kind of preparation method of metal hydride/nano carbon composite material |
| CN106957046B (en) * | 2017-05-27 | 2019-08-27 | 河南纳宇新材料有限公司 | A kind of improvement technique preparing α-three aluminum hydride |
| CN109734053B (en) * | 2019-03-26 | 2022-03-01 | 哈尔滨工业大学 | Aluminum trihydride preparation method based on recycling of ether solvent |
| CN115650264B (en) * | 2022-11-28 | 2023-03-21 | 研峰科技(北京)有限公司 | Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process |
-
1987
- 1987-12-23 CN CN 87101196 patent/CN1011218B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1033610A (en) | 1989-07-05 |
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