CN108946665A - A kind of preparation method and detection method of deuterate aluminium lithium - Google Patents
A kind of preparation method and detection method of deuterate aluminium lithium Download PDFInfo
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- CN108946665A CN108946665A CN201710371767.9A CN201710371767A CN108946665A CN 108946665 A CN108946665 A CN 108946665A CN 201710371767 A CN201710371767 A CN 201710371767A CN 108946665 A CN108946665 A CN 108946665A
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- 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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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
- G01N7/14—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference
- G01N7/18—Analysing materials by measuring the pressure or volume of a gas or vapour by allowing the material to emit a gas or vapour, e.g. water vapour, and measuring a pressure or volume difference by allowing the material to react
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Abstract
The invention discloses a kind of preparation method of deuterate aluminium lithium and active deuterium content measuring methods, comprising the following steps: (1) lithium deuteride is added into ether under conditions of reflux, after mixing evenly, aluminum trichloride (anhydrous) is added, continues to stir；(2) temperature is risen to 25-35 DEG C, reacted 5-7 hours；(3) ether is distilled out, deuterate aluminium lithium is obtained.Deuterate aluminium lithium activity deuterium content made from the preparation method is high, and the mild safety of reaction condition is higher.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, in particular to the preparation method and detection method of deuterated lithium aluminium hydride reduction.
Background technique
Deuterate aluminium lithium is a kind of special fine chemical product, has extremely strong reproducibility, it can be also in organic synthesis
Former aldehyde, ketone, ketenes, cyclic ketones and bicyclic ketone can restore the carboxylic acid derivates such as acid anhydrides, cyclic anhydride and acyl chlorides, can restore primary amide, tertiary acyl
Amine, aliphatic nitro compound, ester, lactone, sulfur-containing compound, sulfonic acid, halogenated aryl hydrocarbon, epoxides, it is in region or solid
Excellent characteristic is shown in selective reduction.With the rapid development of our country's economy, the demand of this product is increasingly increased.Deuterate aluminium
Lithium generally uses lithium deuteride and bromination reactive aluminum to be made, and the chemical property of aluminium bromide is more active, meets water and hydrolyzes, heat resolve,
And reaction condition is affected to the active deuterium content of final deuterate aluminium lithium obtained, temperature controls bad easily bumping and causes to endanger
Danger.This field needs a kind of deuterate aluminium lithium preparation method that convenient, fast and active deuterium content is high.Active deuterium in deuterate aluminium lithium
Content determines its reducing property, and the content of active deuterium is detected with diffraction approach in existing deuterate aluminium lithium, but can only qualitative detection, nothing
Method accomplishes that quantitatively application condition is big.
Summary of the invention
It is an object of that present invention to provide a kind of preparation method of deuterate aluminium lithium, deuterate aluminium lithium activity deuterium content obtained is high,
The mild safety of reaction condition is higher.
Technical scheme is as follows:
A kind of preparation method of deuterate aluminium lithium, comprising the following steps:
(1) lithium deuteride is added into ether under conditions of reflux, after mixing evenly, aluminum trichloride (anhydrous) is added, continues
Stirring；
(2) temperature is risen to 25-35 DEG C, reacted 5-7 hours；
(3) ether is distilled out, deuterate aluminium lithium is obtained.
The mass ratio of the lithium deuteride and aluminum trichloride (anhydrous) is 100:330-380, preferably 100:330, the deuterate
The mass volume ratio of lithium and ether is 100:1200-1700, preferably 100:1200.
The reaction temperature is preferably 32 DEG C, and the reaction time is 6 hours.
The present invention also provides a kind of measuring methods of deuterium content active in deuterate aluminium lithium, measure the content of active deuterium,
Principle is can be reacted with water according to deuterate aluminium lithium, therefore release gas volume after can reacting according to sample with water to calculate sample
Active deuterium content.
LiAlD4+4H2O→LiOH+2D2↑+2H2↑+Al(OH)3
Calculation formula:
V in formula1: before sample is not reacted with water in system gas total volume ml
V2: the volume of gas ml after sample is reacted with water in system
Pt: the atmospheric pressure Pa of environment when measurement
PWater: the saturated vapor pressure Pa of water when measurement under environment temperature
T0: the temperature 273K under standard state
Tt: survey temperature (273+ room temperature) K of timing hierarchy
P0: the gas pressure 1013.2472Pa under standard state
W: the weight g of sample
22400: constant, volume of any gas of 1 gram molecule in standard state.
41.98: the molecular weight of deuterate aluminium lithium
The measuring method comprises the steps of:
(1) the conical flask correct amount for taking a dried and clean, weighs sample and is put into conical flask, covers plug sternly, is denoted as W；
(2) mixed liquor of water and dioxane is added in constant pressure funnel；
(3) constant pressure funnel is connected to become closed system with the conical flask and gas constant pressure capacity tester that sample is housed,
The volume number for writing down the graded tube in gas constant pressure capacity tester, is denoted as V1；
(4) conical flask equipped with sample is placed in ice-water bath；
(5) by constant pressure funnel water and dioxane mixed liquor be added on the sample of conical flask；
(6) sample and water stand 15 minutes in ice-water bath after completion of the reaction, then stand 30 minutes at normal temperature, record
The volume number of graded tube in lower gas constant pressure capacity tester, is denoted as V2；
(7) volume of graded tube after reaction is subtracted the volume before reaction is that deuterate aluminium lithium reacts the gas released with water
Volume.
Water in the step (2): the volume ratio of dioxane is 5:5.
The beneficial effects of the present invention are: the aluminium bromide that the present invention is conventional using cheap aluminum trichloride (anhydrous) substitution,
Safety is more preferable, and temperature control, at 25-35 DEG C, reaction condition is mild, high income, and reachable 99%, the active deuterium of deuterate aluminium lithium
Content is higher, up to 99%.After raw material lithium deuteride inventory determines, according to reaction formula 4LiD+AlCl3→LiAlD4, tri-chlorination
Aluminium amount ratio theoretical value in shortage 10% or so, just can guarantee complete reaction.Solvent ether dosage is reasonable, and very little have yield
It influences.
Specific embodiment
Embodiment 1
A kind of preparation method of deuterate aluminium lithium, comprising the following steps:
(1) lithium deuteride 100g is added into the ether of 1700mL under conditions of reflux, after mixing evenly, is added anhydrous three
Aluminium chloride 372g continues to stir；
(2) temperature is risen to 25 DEG C, reacted 5 hours；
(3) ether is distilled out, deuterate aluminium lithium is obtained.
Embodiment 2-8
Step is shown in Table 1 with embodiment 1, reactant dosage and reaction condition.
Embodiment 9
The measuring method of active deuterium content in deuterate aluminium lithium made from embodiment 1-8:
(1) the conical flask correct amount for taking a dried and clean, weighs sample and is put into conical flask, covers plug sternly, is denoted as W；
(2) mixed liquor (water: the volume ratio of dioxane is 5:5) of water and dioxane is added in constant pressure funnel；
(3) constant pressure funnel is connected to become closed system with the conical flask and gas constant pressure capacity tester that sample is housed,
The volume number for writing down the graded tube in gas constant pressure capacity tester, is denoted as V1；
(4) conical flask equipped with sample is placed in ice-water bath；
(5) by constant pressure funnel water and dioxane mixed liquor be added on the sample of conical flask；
(6) sample and water stand 15 minutes in ice-water bath after completion of the reaction, then stand 30 minutes at normal temperature, record
The volume number of graded tube in lower gas constant pressure capacity tester, is denoted as V2；
(7) volume of graded tube after reaction is subtracted the volume before reaction is that deuterate aluminium lithium reacts the gas released with water
Volume.
The comparison of 1 deuterate aluminium lithium reaction condition of table
From examples it can be seen that the yield of lithium deuteride is most when the amount ratio theoretical value of alchlor is less than 10%
Height, and active deuterium content also reaches 99% or more, the dosage of ether is also larger on the yield of lithium deuteride and active deuterium content influence,
Dosage is too small, is unfavorable for sufficiently reacting, and dosage is excessive to will also result in waste and the high problem of product recycling energy consumption.Only when
Lithium deuteride reacts best when 100:1200-1700 (g/mL) with the mass volume ratio of ether.
Claims (5)
1. a kind of preparation method of deuterate aluminium lithium, which comprises the following steps:
(1) lithium deuteride is added into ether under conditions of reflux, after mixing evenly, aluminum trichloride (anhydrous) is added, continues to stir；
(2) temperature is risen to 25-35 DEG C, reacted 5-7 hours；
(3) ether is distilled out, deuterate aluminium lithium is obtained.
2. preparation method as described in claim 1, which is characterized in that the mass ratio of the lithium deuteride and aluminum trichloride (anhydrous) is
The mass volume ratio of 100:330-380, preferably 100:330, the lithium deuteride and ether is 100:1200-1700, preferably
100:1200。
3. preparation method as described in claim 1, which is characterized in that the reaction temperature is preferably 32 DEG C, the reaction time 6
Hour.
4. a kind of measuring method of deuterate aluminium lithium activity deuterium content, which is characterized in that comprise the steps of:
(1) the conical flask correct amount for taking a dried and clean, weighs sample and is put into conical flask, covers plug sternly, is denoted as W；
(2) mixed liquor of water and dioxane is added in constant pressure funnel；
(3) constant pressure funnel is connected to become closed system with the conical flask and gas constant pressure capacity tester that sample is housed, write down
The volume number of graded tube in gas constant pressure capacity tester, is denoted as V1；
(4) conical flask equipped with sample is placed in ice-water bath；
(5) by constant pressure funnel water and dioxane mixed liquor be added on the sample of conical flask；
(6) sample and water stand 15 minutes in ice-water bath after completion of the reaction, then stand 30 minutes at normal temperature, record gas
The volume number of graded tube in body constant pressure capacity tester, is denoted as V2；
(7) volume of graded tube after reaction is subtracted the volume before reaction is that deuterate aluminium lithium reacts the gas body released with water
Product.
5. measuring method as claimed in claim 4, water in the step (2): the volume ratio of dioxane is 5:5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358167A (en) * | 2018-02-11 | 2018-08-03 | 庄英俊 | A kind of preparation of deuterate aluminium lithium and detection method |
| RU2700522C1 (en) * | 2018-12-26 | 2019-09-17 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method of producing crystalline lithium-aluminum deuteride |
| CN114890442A (en) * | 2022-06-29 | 2022-08-12 | 理道新材(北京)科技有限公司 | Method for recycling lithium chloride in production process of lithium aluminum deuteride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759215A (en) * | 2014-12-26 | 2015-07-08 | 车荣睿 | Preparation process for lithium aluminum hydride-tetrahydrofuran solution |
-
2017
- 2017-05-24 CN CN201710371767.9A patent/CN108946665A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759215A (en) * | 2014-12-26 | 2015-07-08 | 车荣睿 | Preparation process for lithium aluminum hydride-tetrahydrofuran solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358167A (en) * | 2018-02-11 | 2018-08-03 | 庄英俊 | A kind of preparation of deuterate aluminium lithium and detection method |
| RU2700522C1 (en) * | 2018-12-26 | 2019-09-17 | Акционерное общество "Государственный Ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (АО "ГНИИХТЭОС") | Method of producing crystalline lithium-aluminum deuteride |
| CN114890442A (en) * | 2022-06-29 | 2022-08-12 | 理道新材(北京)科技有限公司 | Method for recycling lithium chloride in production process of lithium aluminum deuteride |
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Application publication date: 20181207 |