CN109970030B - Synthesis process of alpha-aluminum trihydride - Google Patents
Synthesis process of alpha-aluminum trihydride Download PDFInfo
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- CN109970030B CN109970030B CN201910316282.9A CN201910316282A CN109970030B CN 109970030 B CN109970030 B CN 109970030B CN 201910316282 A CN201910316282 A CN 201910316282A CN 109970030 B CN109970030 B CN 109970030B
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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
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
Abstract
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a synthesis process of alpha-aluminum trihydride. The invention provides a preparation method of aluminum trihydride, ether solvent used in synthesis can be directly recycled without distillation process, and raw material cost of alpha-aluminum trihydride is reduced. The recovered ether solvent can be directly recovered for reuse without distillation, and the energy consumption level of the alpha-aluminum trihydride de crystallization reaction process is reduced.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage materials, and particularly relates to a synthesis process of alpha-aluminum trihydride.
Background
Alpha-aluminium trihydride (alpha-AlH)3) Is binary covalent hydride, and the volume hydrogen storage is 0.148kg H2The hydrogen storage capacity reaches 10.08 percent, has higher hydrogen storage capacity, and can be applied to propellants, explosives, reducing agents, hydrogen fuel cells and atomic layer depositionProduct technique, etc. The aluminum trihydride has heterogeneity, and the unsolvated aluminum trihydride has seven different crystal forms, namely alpha-AlH3、β-AlH3、γ-AlH3、δ-AlH3、ε-AlH3、θ-AlH3、α’-AlH3Wherein the aluminum trihydride is present in alpha-AlH3、β-AlH3And gamma-AlH3The existence of three crystal forms is dominant, and in the seven crystal forms, alpha-AlH3Has the most stable structure and can stably exist in air. alpha-AlH of current utility3The synthesis method is mainly based on "wet" synthesis (the Journal of the American Chemical Society, 1976, pp.2450-2453), i.e., a suitable amount of LiAlH4And AlCl3
3LiAlH4+AlCl3→4AlH3·nEt2O+3LiCl (1)
AlH3·nEt2O→AlH3+nEt2O (2)
Reacting in ether solution to generate aluminum trihydride ether complex (1), and then refluxing in nonpolar solvent (toluene, xylene, etc.) with higher boiling point to remove ether and crystallize to obtain (2). The intermediate aluminum trihydride ethyl ether complex generated in the method is easy to crystallize and separate out in the solvent ethyl ether to block pipelines and valves of a reaction device, so a large amount of ethyl ether solvent is required to be used for keeping the aluminum trihydride ethyl ether complex in a dissolved state in the synthesis process. The solubility of the intermediate aluminum trihydride ethyl ether complex is reduced along with the rise of the temperature, and low-temperature refrigeration equipment is needed to keep the solution at a low temperature (-15 ℃ to-10 ℃) so that the aluminum trihydride ethyl ether complex is in a dissolved state after being filtered, so the reaction process needs to be provided with the low-temperature refrigeration equipment, and the energy consumption of the synthesis process is larger. Due to AlH3The ether complex has limited solubility in ether, resulting in low single-batch yield of the compound, and the solvent ether is distilled off during the de-etherification process, which consumes a large amount of energy, resulting in high energy consumption during the synthesis process. Literature (Preparation, characterization and composition of gamma-and alpha-alkane AlH)3AIAA 2011-5583) reports that AlH will be prepared3Diethyl ether in diethyl ether complex solution under reduced pressureEvaporating to dryness, grinding the obtained solid aluminum trihydride ethyl ether complex, and then carrying out solid phase de-etherification in a vacuum oven or toluene, wherein the method needs a special ethyl ether distillation and recovery device and a reduced pressure vacuum extractor, and simultaneously solid AlH3The solid powder of ether complex requires a grinding process and is liable to catch fire during handling, resulting in a high safety risk of the process. Therefore, the development of the synthesis process for reducing the investment cost of alpha-aluminum trihydride preparation equipment, reducing the energy consumption level of the alpha-aluminum trihydride synthesis process and improving the safety risk of the alpha-aluminum trihydride synthesis process is of great significance for large-scale preparation and application of alpha-aluminum trihydride.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the synthesis process of the alpha-aluminum trihydride overcomes the defects of the prior art, overcomes the problem that an intermediate aluminum trihydride ether complex is easy to separate out and uses a large amount of ether solvent, does not need a low-temperature refrigeration device configured for keeping the dissolution of the aluminum trihydride ether complex, reduces the equipment cost and the energy consumption level of the synthesis process in the reaction process, can directly recycle and reuse the recycled ether solvent without a distillation process, reduces the energy consumption level of the alpha-aluminum trihydride de ether crystallization reaction process, and improves the single-batch yield of the alpha-aluminum trihydride.
The technical solution of the invention is as follows:
a process for the synthesis of alpha-aluminum trihydride, the process comprising the steps of:
(1) mixing diethyl ether solution of anhydrous aluminum trichloride and diethyl ether solution of lithium aluminum hydride to react, and protecting by using inert gas in the reaction process, wherein the reaction temperature is-10-0 ℃, stirring in the reaction process, and the reaction time is 30-60 min; the inert gas is nitrogen, and a mixture is obtained after the reaction is finished; the stirring speed is 30-80 r/min;
(2) filtering the mixture obtained in the step (1) to remove a filter cake, wherein the filter cake is a byproduct lithium chloride;
(3) heating the filtrate obtained in the step (2), stirring or ultrasonically treating the filtrate in the heating process, wherein the heating temperature is 10-25 ℃, the heating time is 20-40min, obtaining aluminum trihydride ether complex slurry, standing, layering after standing, wherein the upper layer is an ether solvent, and the ether solvent is transferred to a reaction bottle for reuse; the stirring speed is 30-80 r/min;
(4) conveying the lower-layer product obtained in the step (3) into toluene at 82-88 ℃ for de-etherification and separation, filtering, washing a filter cake with distilled water and then with ether, and drying after washing to obtain alpha-aluminum trihydride;
in the step (1), the molar ratio of the volume of the anhydrous ether solvent added to the anhydrous ether solution of aluminum trichloride to the anhydrous aluminum trichloride is 0.4-0.6L: 1 mol;
in the aether solution of lithium aluminum hydride, the molar ratio of the volume of the added anhydrous aether solvent to the lithium aluminum hydride is 0.3L-0.7L: 1 mol; the molar ratio of the lithium aluminum hydride to the anhydrous aluminum trichloride is 3.2-4: 1;
in the step (3), the ultrasonic power is 100-500W;
in the step (4), the molar ratio of the volume of the toluene to the anhydrous aluminum trichloride in the step (1) is 0.5-0.8L: 1 mol.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a preparation method of aluminum trihydride, ether solvent used in synthesis can be directly recycled without distillation process, and raw material cost of alpha-aluminum trihydride is reduced. The recovered ether solvent can be directly recovered for reuse without distillation, and the energy consumption level of the alpha-aluminum trihydride de crystallization reaction process is reduced.
(2) The synthesis process does not need to keep the aluminum trihydride ethyl ether complex intermediate in a dissolved and clear state, does not need to use energy-consuming low-temperature refrigeration equipment to preserve heat, and reduces the equipment cost and the energy consumption level of the synthesis process.
(3) The process can increase LiAlH4And AlCl3The unit volume feeding amount of the aluminum trihydride can improve the single-batch yield of the aluminum trihydride under the same equipment condition.
(4) The method comprises the steps of mixing an aluminum trichloride ether solution and an aluminum lithium hydride ether solution to prepare an aluminum trihydride ether complex solution, filtering to remove a byproduct lithium chloride, heating a filtrate to 10-25 ℃ under stirring or ultrasonic conditions to form an aluminum trihydride ether complex slurry system, standing, transferring ether to a reaction bottle for reuse, conveying the remaining slurry aluminum trihydride ether complex to high-temperature toluene for removing ether and separating out, filtering, washing solid particles with distilled water and ethanol, and drying to obtain an alpha-aluminum trihydride product. The invention can improve the single-batch yield of the aluminum trihydride under the same equipment condition. The ether solvent used in the synthesis can be directly recycled without distillation process, thereby reducing the raw material cost of the alpha-aluminum trihydride. The aluminum trihydride complex ether solution is not insulated by using energy-consuming low-temperature refrigeration equipment, so that the equipment cost and the energy consumption level of the synthesis process are reduced.
Detailed Description
Example 1
45 g of lithium aluminium hydride in 0.38L of anhydrous ether and 48 g of AlCl3Dissolving in 0.15L of anhydrous ether, introducing nitrogen for protection, mixing and stirring the aluminum trichloride ether solution and the aluminum lithium hydride ether solution for 30 minutes at the temperature of-10 ℃, filtering to remove a by-product lithium chloride after reaction is stopped, heating the filtrate to 15 ℃ aluminum trihydride ether complex slurry under the stirring condition of 30 r/min, stopping stirring after 20 minutes, standing, transferring 0.37L of upper-layer ether solvent, transferring the remaining aluminum trihydride ether complex slurry to 82 ℃ 0.19L of toluene for removing ether, cooling the reaction system to room temperature after the ether which is not condensed in a condenser is distilled out, filtering, washing with distilled water and ethanol, and drying to obtain 30.6 g of alpha-aluminum trihydride product.
Example 2
49 g of lithium aluminium hydride in 0.65L of anhydrous ether and 48 g of AlCl3Dissolving in 0.18L anhydrous ether, introducing nitrogen gas for protection, mixing and stirring aluminum trichloride ether solution and lithium aluminum hydride ether solution at-8 deg.C for 40min, filtering to remove byproduct lithium chloride after reaction, stirring at 50 r/minThe filtrate was heated to 10 ℃ to form aluminum trihydride etherate slurry, stirring was stopped after 30 minutes, and 0.57L of the upper etherate solvent was transferred after standing. Transferring the residual aluminum trihydride ether complex slurry into 0.19L toluene at 84 ℃ for deetherification, cooling the reaction system to room temperature after ether which is not condensed in a condenser is distilled out, filtering, washing with distilled water and ethanol, and drying to obtain 31.6 g of alpha-aluminum trihydride product.
Example 3
52 g of lithium aluminum hydride are dissolved in 0.82L of anhydrous ether, and 48 g of AlCl are added3Dissolving in 0.2L of anhydrous ether, introducing nitrogen for protection, mixing and stirring the aluminum trichloride ether solution and the aluminum lithium hydride ether solution for 45 minutes at the temperature of-5 ℃, filtering to remove a by-product lithium chloride after reaction is stopped, heating the filtrate to 20 ℃ under the stirring condition of 80 r/min, stopping stirring after 40 minutes, standing and transferring 0.87L of upper-layer ether solvent. Transferring the residual aluminum trihydride ether complex slurry into 0.25L toluene at 86 ℃ for de-etherification, cooling the reaction system to room temperature after ether which is not condensed in a condenser is distilled out, filtering, washing with distilled water and ethanol, and drying to obtain 31.4 g of alpha-aluminum trihydride product.
Example 4
54 g of lithium aluminium hydride are dissolved in 0.95L of anhydrous ether, and 48 g of AlCl are added3Dissolving in 0.21L of anhydrous ether, introducing nitrogen for protection, mixing and stirring the aluminum trichloride ether solution and the aluminum lithium hydride ether solution for 50 minutes at the temperature of-3 ℃, filtering to remove a byproduct lithium chloride after reaction is stopped, heating the filtrate to 25 ℃ of aluminum trihydride ether complex slurry under the ultrasonic condition of 100W, stopping ultrasonic treatment after 30 minutes, standing, and transferring 0.95L of upper ether solvent. Transferring the residual aluminum trihydride ether complex slurry into 0.28L toluene at 87 ℃ for de-etherification, cooling the reaction system to room temperature after ether which is not condensed in a condenser is distilled out, filtering, washing with distilled water and ethanol, and drying to obtain 32.3 g of alpha-aluminum trihydride product.
Example 5
46 grams of lithium aluminum hydride was dissolved in 0.61L of anhydrous sodium hydroxideDiethyl ether, 48 g AlCl3Dissolving in 0.18L of anhydrous ether, introducing nitrogen for protection, mixing and stirring the aluminum trichloride ether solution and the aluminum lithium hydride ether solution for 60 minutes at the temperature of-1 ℃, filtering to remove a byproduct lithium chloride after reaction is stopped, heating the filtrate to 20 ℃ of aluminum trihydride ether complex slurry under the ultrasonic condition of 400W, stopping ultrasonic after 20 minutes, standing, and transferring 0.64L of upper-layer ether solvent. Transferring the residual aluminum trihydride ether complex slurry into 0.25L toluene at 88 ℃ for de-etherification, cooling the reaction system to room temperature after ether which is not condensed in a condenser is distilled out, filtering, washing with distilled water and ethanol, and drying to obtain 31 g of alpha-aluminum trihydride product.
Claims (1)
1. A process for the synthesis of alpha-aluminium trihydride, characterized in that it comprises the steps of:
(1) mixing diethyl ether solution of anhydrous aluminum trichloride and diethyl ether solution of lithium aluminum hydride for reaction at the temperature of-10-0 ℃ for 30-60min, stirring at the stirring speed of 30-80 r/min in the reaction process, protecting by using inert gas in the reaction process, and obtaining a mixture after the reaction is finished;
in the ether solution of anhydrous aluminum trichloride, the molar ratio of the volume of the added anhydrous ether solvent to the anhydrous aluminum trichloride is 0.4-0.6L: 1 mol;
in the aether solution of lithium aluminum hydride, the molar ratio of the volume of the added anhydrous aether solvent to the lithium aluminum hydride is 0.3L-0.7L: 1 mol; the molar ratio of the lithium aluminum hydride to the anhydrous aluminum trichloride is 3.2-4: 1.
(2) filtering the mixture obtained in the step (1), removing a filter cake, heating the filtrate at 10-25 ℃ for 20-40min to obtain aluminum trihydride ethyl ether complex slurry, and standing; stirring or ultrasonically treating the filtrate in the heating process, wherein the stirring speed is 30-80 revolutions per minute, and the ultrasonic power is 100-500W;
(3) conveying the lower-layer product obtained in the step (2) into toluene for de-etherification and separation, filtering, washing a filter cake with distilled water, then washing with diethyl ether, and drying after washing to obtain alpha-aluminum trihydride;
the molar ratio of the volume of the toluene to the anhydrous aluminum trichloride in the step (1) is 0.5-0.8L: 1mol, the temperature of the toluene is 82-88 ℃.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106335877A (en) * | 2015-09-17 | 2017-01-18 | 湖北航天化学技术研究所 | Synthesis method of fine-grained alpha-AlH3 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106335877A (en) * | 2015-09-17 | 2017-01-18 | 湖北航天化学技术研究所 | Synthesis method of fine-grained alpha-AlH3 |
Non-Patent Citations (4)
| Title |
|---|
| NMR spectroscopic and thermodynamic studies of the etherate and the α, α’, and r phases of AlH3;Terry D. Humphries et al.;《i n t e r n a t i o n a l j ournal o f hydrogen energy》;20130305;第38卷;第4577-4586页 * |
| Preparation and thermal properties of aluminum hydride polymorphs;Bo Xu et al.;《Vacuum》;20141231;第99卷;表1，第134页左栏第2段，图6d * |
| Thermal properties of AlH3-etherate and its desolvation reaction into AlH3;T. Kato et al.;《Journal of Alloys and Compounds》;20070330;第276-279页 * |
| 高纯α-AlH3的合成及表征;张永岗等;《武汉理工大学学报》;20121130;第34卷(第11期);第11页1.2-1.3 * |
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