CN108358167A - A kind of preparation of deuterate aluminium lithium and detection method - Google Patents
A kind of preparation of deuterate aluminium lithium and detection method Download PDFInfo
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- CN108358167A CN108358167A CN201810140586.XA CN201810140586A CN108358167A CN 108358167 A CN108358167 A CN 108358167A CN 201810140586 A CN201810140586 A CN 201810140586A CN 108358167 A CN108358167 A CN 108358167A
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- 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 product content assay methods, include the following steps：(1) lithium deuteride is added into ether under conditions of reflux, after stirring evenly, aluminum trichloride (anhydrous) is added, continues to stir；(2) temperature is risen to 25 35 DEG C, reacted 5.5 7 hours；(3) ether is distilled out, deuterate aluminium lithium is obtained.Deuterate aluminium lithium product content made from the preparation method is high, and reaction condition is mild, safety higher.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, more particularly to the preparation method and detection method of deuterated lithium aluminium hydride reduction.
Background technology
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 fast development of China's economy, the demand to this product increasingly increases.Deuterate aluminium
Lithium generally uses lithium deuteride to be made with bromination reactive aluminum, 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.There is an urgent need for the high deuterate aluminium lithium preparation methods of a kind of convenient, fast and active deuterium content for this field.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 to quantify, and application condition is big.
Invention content
Present invention aims at provide a kind of preparation method suitable for industrialized production deuterate aluminium lithium, deuterate aluminium obtained
Lithium product content is high, the mild safety higher of reaction condition.
Technical scheme is as follows：
A kind of preparation method of deuterate aluminium lithium, includes the following steps：
(1) lithium deuteride is added into ether under conditions of reflux, after stirring evenly, aluminum trichloride (anhydrous) is added, continues
Stirring；
(2) temperature is risen to 25-35 DEG C, synthesis under normal pressure 5.5-7 hours；
(3) ether is distilled out, deuterate aluminium lithium is obtained.
The mass ratio of the wherein described lithium deuteride and aluminum trichloride (anhydrous) is 100：330-372, the lithium deuteride and ether
Mass volume ratio is 100：1200-1700.
Further, the mass ratio of the lithium deuteride and aluminum trichloride (anhydrous) is 100：330.
Further, the mass volume ratio of the lithium deuteride and ether is 100：1700.
Further, the reaction temperature is preferably 32 DEG C, and the reaction time is 6.1 hours.
It should be noted that lithium deuteride diethyl ether solution in lithium deuteride and aluminum trichloride (anhydrous) amount ratio, the dosage of ether,
The reaction temperature of lithium deuteride and aluminum trichloride (anhydrous), the reaction time is for the yield and its deuterate aluminium lithium of the deuterate aluminium lithium prepared
After product content has very crucial influence, raw material lithium deuteride inventory to determine, alchlor must be more in shortage than theoretical value
10% or so, it just can guarantee complete reaction, solvent ether should be in 1700ml or so, and very little have an impact yield, preferred to use
For amount proportioning under the reaction time, the high income and deuterate aluminium lithium product content of the deuterate aluminium lithium obtained are preferable.
The present invention also provides a kind of assay methods of deuterate aluminium lithium product content, measure the content of deuterate aluminium lithium product,
Its principle is can be reacted with water according to deuterate aluminium lithium, therefore release gas volume after being reacted with water according to sample to calculate sample
Content,
LiAlD4+4H2O→LiOH+2D2↑+2H2↑+Al(OH)3
Institute of the invention in addition disclosed in a kind of assay method of deuterate aluminium lithium product content, include the following steps：
1) the conical flask correct amount for taking a dried and clean weighs deuterate aluminium lithium sample and is put into conical flask, and capping plug is tight,
Deuterate aluminium lithium sample is denoted as W；
2) mixed liquor of water and dioxane is added in constant pressure funnel；
3) constant pressure funnel is connected with the conical flask and gas constant pressure capacity tester that the deuterate aluminium lithium sample is housed
It is connected into as closed system, writes down the volume number of the graded tube in the gas constant pressure capacity tester, be denoted as V1；
4) conical flask equipped with the deuterate aluminium lithium sample is placed in ice-water bath；
5) by the constant pressure funnel water and dioxane mixed liquor be added on the deuterate aluminium lithium sample of the conical flask；
6) the deuterate aluminium lithium sample stands 15 minutes in ice-water bath after completion of the reaction with water, then stands at normal temperatures
30 minutes, the volume number of the graded tube in the gas constant pressure capacity tester is recorded, V is denoted as2；
7) volume of graded tube after reaction is subtracted to the volume V before reaction2-V1As deuterate aluminium lithium reacts releasing with water
Gas volume；
8) it is obtained according to formula
V in formula1：Before sample is not reacted with water in system gas total volume ml；
V2：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：Temperature 273K under standard state；
Tt：Survey temperature (273+ room temperatures) K of timing hierarchy；
P0：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.
Further, water in the step (2)：The volume ratio of dioxane is 5：5.
The beneficial effects of the invention are as follows：The present invention substitutes conventional aluminium bromide using cheap aluminum trichloride (anhydrous),
Safety is more preferable, and temperature control, at 25-35 DEG C, reaction condition is mild, high income, and up to 98%, deuterate aluminium lithium product contains
Amount is higher, up to 98%.After raw material lithium deuteride inventory determines, according to reaction formula 4LiD+AlCl3→LiAlD4, alchlor
Amount ratio theoretical value in shortage 10% or so, just can guarantee complete reaction.Solvent ether dosage is reasonable, if dosage very little can be right
Yield has an impact.
Description of the drawings
In the accompanying drawings：
Fig. 1 is the preparation flow figure of deuterate aluminium lithium.
Fig. 2 is the flow chart of the assay method of deuterate aluminium lithium product content.
Specific implementation mode
Embodiment 1
A kind of preparation method of deuterate aluminium lithium, includes the following steps：
(1) lithium deuteride 100g is added into the ether of 1700mL under conditions of reflux, after stirring evenly, is added anhydrous three
Aluminium chloride 372g continues to stir；
(2) temperature is risen to 25 DEG C, reacted 7 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 assay method of deuterate aluminium lithium product content made from embodiment 1-8：
1) the conical flask correct amount for taking a dried and clean weighs deuterate aluminium lithium sample and is put into conical flask, and capping plug is tight,
Deuterate aluminium lithium example weight is denoted as W；
2) by the mixed liquor (water of water and dioxane：The volume ratio of dioxane is 5:5) it is added in constant pressure funnel；
3) constant pressure funnel is connected to become envelope with the conical flask and gas constant pressure capacity tester that deuterate aluminium lithium sample is housed
Closure system writes down the volume number of the graded tube in gas constant pressure capacity tester, is denoted as V1；
4) conical flask equipped with deuterate aluminium lithium sample is placed in ice-water bath；
5) by constant pressure funnel water and dioxane mixed liquor be added on the deuterate aluminium lithium sample of conical flask；
6) sample stands 15 minutes in ice-water bath after completion of the reaction with water, then takes out and stands 30 points at normal temperatures again
Clock records the volume number of the graded tube in gas constant pressure capacity tester, is denoted as V2；
7) volume of graded tube after reaction is subtracted to the volume V before reaction2-V1As deuterate aluminium lithium reacts releasing with water
Gas volume；
8) it is obtained according to formula
V in formula1：Before sample is not reacted with water in system gas total volume ml；
V2：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：Temperature 273K under standard state；
Tt：Survey temperature (273+ room temperatures) K of timing hierarchy；
P0：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.
1 deuterate aluminium lithium reaction condition of table compares
From examples it can be seen that when the amount ratio theoretical value of alchlor is less than 10%, the yield of lithium deuteride is most
Height, and deuterate aluminium lithium product content also reaches 98% or more, the dosage of ether contains the yield and deuterate aluminium lithium product of lithium deuteride
Amount influences also larger, and dosage is too small, is unfavorable for fully reacting, and dosage is excessive to will also result in waste and product recycling high energy consumption
Problem.Only when the mass volume ratio in lithium deuteride and ether is 100:It is reacted when 1700 (g/mL) best.
Claims (6)
1. a kind of preparation method of deuterate aluminium lithium, includes the following steps：
(1) lithium deuteride is added into ether under conditions of reflux, after stirring evenly, aluminum trichloride (anhydrous) is added, continues to stir；
(2) temperature is risen to 25-35 DEG C, synthesis under normal pressure 5.5-7 hours；
(3) ether is distilled out, deuterate aluminium lithium is obtained；
The mass ratio of the wherein described lithium deuteride and aluminum trichloride (anhydrous) is 100：330-372, the quality of the lithium deuteride and ether
Volume ratio is 100：1200-1700.
2. the preparation method of deuterate aluminium lithium as described in claim 1, wherein the quality of the lithium deuteride and aluminum trichloride (anhydrous)
Than being 100：330.
3. the preparation method of deuterate aluminium lithium as described in claim 1, wherein the mass volume ratio of the lithium deuteride and ether is
100：1700.
4. the preparation method of deuterate aluminium lithium as described in claim 1, wherein the reaction temperature is 32 DEG C, the reaction time is
6.1 hour.
5. a kind of method measuring deuterate aluminium lithium product content in claim 1-4 comprising following steps：
1) the conical flask correct amount for taking a dried and clean weighs deuterate aluminium lithium sample and is put into conical flask, and capping plug is tight, deuterate
Aluminium lithium sample is denoted as W；
2) mixed liquor of water and dioxane is added in constant pressure funnel；
3) constant pressure funnel is connected into the conical flask and gas constant pressure capacity tester that the deuterate aluminium lithium sample is housed
For closed system, the volume number of the graded tube in the gas constant pressure capacity tester is write down, V is denoted as1；
4) conical flask equipped with the deuterate aluminium lithium sample is placed in ice-water bath；
5) by the constant pressure funnel water and dioxane mixed liquor be added on the deuterate aluminium lithium sample of the conical flask；
6) the deuterate aluminium lithium sample stands 15 minutes in ice-water bath after completion of the reaction with water, then stands 30 points at normal temperatures
Clock records the volume number of the graded tube in the gas constant pressure capacity tester, is denoted as V2；
7) volume of graded tube after reaction is subtracted to the volume V before reaction2-V1As deuterate aluminium lithium reacts the gas released with water
Volume；
8) it is obtained according to formula
V in formula1：Before sample is not reacted with water in system gas total volume ml；
V2：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：Temperature 273K under standard state；
Tt：Survey temperature (273+ room temperatures) K of timing hierarchy；
P0：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.
6. method as described in claim 5, wherein water in the step (2)：The volume ratio of dioxane is 5：5.
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| CN201810140586.XA CN108358167A (en) | 2018-02-11 | 2018-02-11 | A kind of preparation of deuterate aluminium lithium and detection method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102901796A (en) * | 2011-07-28 | 2013-01-30 | 车瀛照 | Gas constant pressure capacity tester |
| CN106698345A (en) * | 2016-12-19 | 2017-05-24 | 车荣睿 | Lithium deuteride production process and purity detection method of lithium deuteride |
| CN106885885A (en) * | 2017-04-14 | 2017-06-23 | 车荣睿 | A kind of assay method of deuterate aluminium lithium activity deuterium content |
| CN106966364A (en) * | 2017-04-14 | 2017-07-21 | 车荣睿 | A kind of synthesis technique of deuterate aluminium lithium |
| CN108946665A (en) * | 2017-05-24 | 2018-12-07 | 庄英俊 | A kind of preparation method and detection method of deuterate aluminium lithium |
-
2018
- 2018-02-11 CN CN201810140586.XA patent/CN108358167A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102901796A (en) * | 2011-07-28 | 2013-01-30 | 车瀛照 | Gas constant pressure capacity tester |
| CN106698345A (en) * | 2016-12-19 | 2017-05-24 | 车荣睿 | Lithium deuteride production process and purity detection method of lithium deuteride |
| CN106885885A (en) * | 2017-04-14 | 2017-06-23 | 车荣睿 | A kind of assay method of deuterate aluminium lithium activity deuterium content |
| CN106966364A (en) * | 2017-04-14 | 2017-07-21 | 车荣睿 | A kind of synthesis technique of deuterate aluminium lithium |
| CN108946665A (en) * | 2017-05-24 | 2018-12-07 | 庄英俊 | A kind of preparation method and detection method of deuterate aluminium lithium |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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