CN1033610A - The synthetic method of lithium aluminum hydride - Google Patents

The synthetic method of lithium aluminum hydride Download PDF

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Publication number
CN1033610A
CN1033610A CN 87101196 CN87101196A CN1033610A CN 1033610 A CN1033610 A CN 1033610A CN 87101196 CN87101196 CN 87101196 CN 87101196 A CN87101196 A CN 87101196A CN 1033610 A CN1033610 A CN 1033610A
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lithium
hydride
aluminum hydride
lithium aluminum
dimethylnaphthalene
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CN1011218B (en
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申泮文
张允什
张佳
张大昕
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Nankai University
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Nankai University
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Priority to CN 87101196 priority Critical patent/CN1011218B/en
Publication of CN1033610A publication Critical patent/CN1033610A/en
Publication of CN1011218B publication Critical patent/CN1011218B/en
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    • 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)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the synthetic method of inorganic reagent (lithium aluminum hydride), abroad is to be raw material with the metallic lithium at present, carries out hydrogenation with preparation lithium hydride, the latter and AlCl3 prepared in reaction lithium aluminum hydride under high temperature (680 °-720 ℃) or high pressure (340atm).This method energy consumption in process of production is big, and equipment requirements is high and potential danger arranged.
The used main raw material of the present invention is identical with last method, but reacts under solvent and catalyzer, and entire reaction can be carried out at normal temperatures and pressures.

Description

The synthetic method of lithium aluminum hydride
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.Pat2,576,311) first, it is a kind of urgently 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.S3 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 Schl-esinger 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), 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, the slightly basic naphthalene-titanium tetrachloride of 7-two 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 No2,169-172(1982)

Claims (2)

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, be to use that [(I+II) (I can be naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1 as catalyzer, 6-dimethylnaphthalene, 2,7-dimethylnaphthalene, 2,3-dimethylnaphthalene, 2,3-dimethylnaphthalene, biphenyl, terphenyl, anthracene; II can be titanium tetrachloride or vanadium tetrachloride], use tetrahydrofuran (THF) to make solvent, can carry out at normal temperatures and pressures during hydrogenation.
2, said by metallic lithium and Preparation of Hydrogen lithium hydride according to claim 1, the latter and aluminum trichloride (anhydrous) reaction and prepare the method for lithium aluminum hydride is characterized in that its weight ratio that feeds intake is an I when hydrogenation: II: lithium=32: 1: 3.5.
CN 87101196 1987-12-23 1987-12-23 Synthesis of lithium aluminum hydride Expired CN1011218B (en)

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Application Number Priority Date Filing Date Title
CN 87101196 CN1011218B (en) 1987-12-23 1987-12-23 Synthesis of lithium aluminum hydride

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Application Number Priority Date Filing Date Title
CN 87101196 CN1011218B (en) 1987-12-23 1987-12-23 Synthesis of lithium aluminum hydride

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CN1033610A true CN1033610A (en) 1989-07-05
CN1011218B CN1011218B (en) 1991-01-16

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CN 87101196 Expired CN1011218B (en) 1987-12-23 1987-12-23 Synthesis of lithium aluminum hydride

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Cited By (5)

* Cited by examiner, † Cited by third party
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
CN106410210A (en) * 2016-10-31 2017-02-15 复旦大学 Preparation method of metal hydride/nano carbon composite materials
CN106957046A (en) * 2017-05-27 2017-07-18 河南纳宇滤材有限公司 A kind of modified technique for preparing the aluminum hydrides of α tri-
CN109734053A (en) * 2019-03-26 2019-05-10 哈尔滨工业大学 A kind of three aluminum hydride preparation methods based on recycling ether solvent
CN115650264A (en) * 2022-11-28 2023-01-31 研峰科技(北京)有限公司 Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process

Cited By (7)

* Cited by examiner, † Cited by third party
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
CN106410210A (en) * 2016-10-31 2017-02-15 复旦大学 Preparation method of metal hydride/nano carbon composite materials
CN106410210B (en) * 2016-10-31 2019-08-09 复旦大学 A kind of preparation method of metal hydride/nano carbon composite material
CN106957046A (en) * 2017-05-27 2017-07-18 河南纳宇滤材有限公司 A kind of modified technique for preparing the aluminum hydrides of α tri-
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
CN109734053A (en) * 2019-03-26 2019-05-10 哈尔滨工业大学 A kind of three aluminum hydride preparation methods based on recycling ether solvent
CN115650264A (en) * 2022-11-28 2023-01-31 研峰科技(北京)有限公司 Method for efficiently recovering lithium chloride from lithium aluminum hydride preparation process

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Publication number Publication date
CN1011218B (en) 1991-01-16

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