CN109734053B - Aluminum trihydride preparation method based on recycling of ether solvent - Google Patents
Aluminum trihydride preparation method based on recycling of ether solvent Download PDFInfo
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- CN109734053B CN109734053B CN201910232817.4A CN201910232817A CN109734053B CN 109734053 B CN109734053 B CN 109734053B CN 201910232817 A CN201910232817 A CN 201910232817A CN 109734053 B CN109734053 B CN 109734053B
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Abstract
A preparation method of aluminum trihydride based on recycling of ether solvent relates to the preparation technology of aluminum trihydride, and aims to solve the problems of high ether consumption and difficult recovery in the process of preparing aluminum trihydride. Reacting the lithium aluminum hydride diethyl ether solution with the aluminum chloride diethyl ether solution, filtering at positive pressure to remove lithium chloride to obtain a diethyl ether solution of an aluminum trihydride etherate, supplementing lithium aluminum hydride, fully settling the etherate, and separating the aluminum trihydride etherate and the diethyl ether solution after filtering; and repeatedly adding lithium aluminum hydride and aluminum chloride diethyl ether solution into the diethyl ether solution, and repeatedly filtering and settling to realize the repeated utilization of the diethyl ether solvent. The invention is suitable for preparing aluminum trihydride.
Description
Technical Field
The invention relates to a preparation technology of aluminum trihydride.
Background
Aluminum trihydride (AlH)3) It has been extensively studied in the field of hydrogen storage and high energy propellants due to its higher hydrogen storage capacity, strong combustion heat release behavior compared to other metal hydrides.
The solvent used to prepare the aluminum trihydride may be tetrahydrofuran or diethyl ether, with diethyl ether being the most common solvent. The reaction system of lithium aluminium hydride and aluminium trichloride as raw materials and the obtaining of aluminium trihydride etherate are all carried out in an ether system. However, according to the current international and domestic reports, ether is used only once in the preparation of aluminum trihydride, cannot be used continuously, and cannot be effectively recovered due to the very low boiling point. The consumption of ether at the laboratory stage is negligible, however, the consumption of ether is substantial in both pilot and pilot experiments.
Disclosure of Invention
The invention aims to solve the problems of high diethyl ether consumption and difficult recovery in the process of preparing aluminum trihydride, and provides a method for preparing aluminum trihydride based on recycling diethyl ether solvent.
The invention relates to a method for preparing aluminum trihydride based on recycling of an ether solvent, which comprises the following steps:
step one, preparing lithium aluminum hydride diethyl ether solution and aluminum chloride diethyl ether solution;
step two, placing the lithium aluminum hydride diethyl ether solution and the aluminum chloride diethyl ether solution in the step one into a reactor for reaction to obtain a solid-liquid mixture, wherein the molar ratio of lithium aluminum hydride to aluminum chloride is 3.5-4.5: 1;
step three, filtering the solid-liquid mixture obtained in the step two at positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
step four, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate in the step three, stirring at room temperature until the etherate is fully settled, and filtering to separate the aluminum trihydride etherate and the ether solution;
step five, adding lithium aluminum hydride into the ether solution obtained in the previous step, stirring and adding an aluminum chloride ether solution for reaction to obtain a solid-liquid mixture;
step six, filtering the solid-liquid mixture obtained in the step five under positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
step seven, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate obtained in the step six, stirring at room temperature until the etherate is fully settled, and filtering to separate the aluminum trihydride etherate and the ether solution;
repeating the fifth step to the seventh step for a plurality of times;
and finally, carrying out crystal transformation and ether removal on the separated aluminum trihydride etherate to obtain the aluminum trihydride.
Preferably, the reaction conditions in the second and fifth steps are at a temperature of-12 ℃ to-10 ℃.
Preferably, the preparation process is carried out under inert gas protection.
Preferably, the preparation process is carried out under anhydrous and oxygen-free conditions.
Preferably, the aperture of the sand core used for positive pressure filtration in the third step and the sixth step is 4-9 μm.
Preferably, in the step one, the solvent diethyl ether of the lithium aluminum hydride diethyl ether solution and the aluminum chloride diethyl ether solution is obtained by removing water by using metal sodium and distilling by using benzophenone as an indicator.
Preferably, steps five to seven are performed 2 times in total.
The invention has the beneficial effects that:
1. the invention provides a method for preparing aluminum trihydride based on recycling of an ether solvent for the first time, and solves the problems of high ether consumption, low economy and environmental protection in the preparation process.
2. The method can realize continuous operation in the process of preparing the aluminum trihydride, is very simple and efficient, and is easy to popularize.
3. The method greatly reduces the dependence on the amount of the diethyl ether, saves the time for pretreating the solvent, reduces the production cost for producing the aluminum trihydride on a large scale, and provides necessary technical support for the large-scale production.
4. The invention can repeatedly use the ether solution, but has no influence on the product.
Drawings
FIG. 1 is a flow chart of a method for producing aluminum trihydride based on recycling of an ether solvent in example 1;
FIG. 2 is an XRD pattern of an aluminum trihydride etherate prepared in example 1;
FIG. 3 is an XRD pattern of a transcrystallized product of aluminum trihydride etherate in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
The first embodiment is as follows: the method for preparing aluminum trihydride based on recycling of ether solvent in the embodiment comprises the following steps:
step one, preparing lithium aluminum hydride diethyl ether solution and aluminum chloride diethyl ether solution;
step two, placing the lithium aluminum hydride diethyl ether solution and the aluminum chloride diethyl ether solution in the step one into a reactor for reaction to obtain a solid-liquid mixture, wherein the molar ratio of lithium aluminum hydride to aluminum chloride is 3.5-4.5: 1;
step three, filtering the solid-liquid mixture obtained in the step two at positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
step four, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate in the step three, stirring at room temperature until the etherate is fully settled, and filtering to separate the aluminum trihydride etherate and the ether solution;
step five, adding lithium aluminum hydride into the ether solution obtained in the previous step, stirring and adding an aluminum chloride ether solution for reaction to obtain a solid-liquid mixture;
step six, filtering the solid-liquid mixture obtained in the step five under positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
step seven, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate obtained in the step six, stirring at room temperature until the etherate is fully settled, and filtering to separate the aluminum trihydride etherate and the ether solution;
repeating the fifth step to the seventh step for a plurality of times;
and finally, carrying out crystal transformation and ether removal on the separated aluminum trihydride etherate to obtain the aluminum trihydride.
The precipitated aluminum trihydride etherate is filtered to separate the aluminum trihydride etherate and ether filtrate; and then, repeatedly adding lithium aluminum hydride and the aluminum trichloride raw material into the ether filtrate to react, and repeating the filtering operation again to realize the repeated utilization of the ether solvent.
The second embodiment is as follows: the difference between the first embodiment and the second embodiment is that the reaction conditions in the second and fifth steps are-12 ℃ to-10 ℃ and the reaction is carried out under the protection of inert gas. Preventing the exothermic heat of reaction from causing the solvent to volatilize and creating a hazard.
The third concrete implementation mode: this embodiment differs from the first embodiment in that the preparation process is carried out under anhydrous and oxygen-free conditions.
The fourth concrete implementation mode: the difference between the first embodiment and the second embodiment is that the aperture of the sand core used for the positive pressure filtration in the third and sixth steps is 4-9 μm.
The fifth concrete implementation mode: the difference between the first embodiment and the second embodiment is that in the first step, the solvent diethyl ether of the lithium aluminum hydride diethyl ether solution and the aluminum chloride diethyl ether solution is obtained by removing water from the metal sodium and distilling the metal sodium by using benzophenone as an indicator. The ether is dewatered to obtain anhydrous ether.
The sixth specific implementation mode: the difference between this embodiment and the first embodiment is that the fifth to seventh steps are performed 2 times.
Example 1:
step one, preparing lithium aluminum hydride diethyl ether solution and aluminum chloride diethyl ether solution;
step two, lithium aluminum hydride (LiAlH) in the step one4) Diethyl ether solution and aluminium chloride (AlCl)3) And (2) putting the ether solution into a reactor, and reacting under the conditions of argon protection, low temperature (-12 ℃ to-10 ℃) and stirring to obtain a solid-liquid mixture, wherein the molar ratio of lithium aluminum hydride to aluminum chloride is 4: 1;
step three, filtering the solid-liquid mixture obtained in the step two at positive pressure, and removing lithium chloride (LiCl) to obtain an ether solution of aluminum trihydride etherate;
step four, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate in the step three, stirring at room temperature until the aluminum trihydride etherate is fully settled, and separating an aluminum trihydride etherate a and the ether solution after filtering;
adding the rest amount of lithium aluminum hydride into the ether solution obtained in the previous step, and adding an aluminum chloride ether solution into the ether solution at a low temperature of (-12 ℃ to-10 ℃) under the stirring condition to perform a second reaction to obtain a solid-liquid mixture;
step six, filtering the solid-liquid mixture obtained in the step five under positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
seventhly, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate obtained in the sixth step, stirring at room temperature until the aluminum trihydride etherate is fully settled, and filtering to separate an aluminum trihydride etherate b and an ether solution;
repeating the operations of the fifth step to the seventh step to obtain the aluminum trihydride etherate c.
The specific flow is shown in figure 1.
In order to check and verify whether the trihydride etherate a, the trihydride etherate b and the trihydride etherate c prepared from different batches are different or not, the X-ray diffraction behavior research is carried out on the trihydride etherate a, the trihydride etherate b and the trihydride etherate c, as shown in fig. 2, it can be seen that the trihydride etherate a, the trihydride etherate b and the trihydride etherate c are not different.
In order to verify whether the aluminum trihydride etherate a, the aluminum trihydride etherate b and the aluminum trihydride etherate c prepared from different batches can be successfully subjected to crystal transformation to obtain aluminum trihydride, the crystal transformation behaviors of the aluminum trihydride etherate a, the aluminum trihydride etherate b and the aluminum trihydride etherate c are studied. FIG. 3 is an XRD pattern of the products obtained by crystallizing aluminum trihydride etherate a, aluminum trihydride etherate b and aluminum trihydride etherate c under the same solid phase vacuum condition, and it can be seen that the products obtained are all the target compound aluminum trihydride.
Claims (7)
1. A method for preparing aluminum trihydride based on recycling of ether solvent is characterized by comprising the following steps:
step one, preparing lithium aluminum hydride diethyl ether solution and aluminum chloride diethyl ether solution;
step two, placing the lithium aluminum hydride diethyl ether solution and the aluminum chloride diethyl ether solution in the step one into a reactor for reaction to obtain a solid-liquid mixture, wherein the molar ratio of lithium aluminum hydride to aluminum chloride is 3.5-4.5: 1;
step three, filtering the solid-liquid mixture obtained in the step two at positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
step four, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate in the step three, stirring at room temperature until the etherate is fully settled, and filtering to separate the aluminum trihydride etherate and the ether solution;
step five, adding lithium aluminum hydride into the ether solution obtained in the previous step, stirring and adding an aluminum chloride ether solution for reaction to obtain a solid-liquid mixture;
step six, filtering the solid-liquid mixture obtained in the step five under positive pressure, and removing lithium chloride to obtain an ether solution of aluminum trihydride etherate;
step seven, adding lithium aluminum hydride into the ether solution of the aluminum trihydride etherate obtained in the step six, stirring at room temperature until the etherate is fully settled, and filtering to separate the aluminum trihydride etherate and the ether solution;
repeating the fifth step to the seventh step for a plurality of times;
and finally, carrying out crystal transformation and ether removal on the separated aluminum trihydride etherate to obtain the aluminum trihydride.
2. The method for preparing aluminum trihydride based on recycling of ether solvents according to claim 1, wherein the reaction conditions in the second step and the fifth step are a temperature of-12 ℃ to-10 ℃.
3. The method for preparing aluminum trihydride based on recycling of ether solvents according to claim 1, wherein the preparation is carried out under inert gas.
4. The method of claim 1, wherein the aluminum trihydride is prepared under anhydrous and oxygen-free conditions.
5. The method for preparing aluminum trihydride based on recycling of ether solvents according to claim 1, wherein positive pressure filtration in the third step and the sixth step adopts a sand core with a pore size of 4-9 μm.
6. The method for preparing aluminum trihydride based on recycling of ether solvents as claimed in claim 1, wherein in the step one, the ether solvents of lithium aluminum hydride ether solution and aluminum chloride ether solution are benzophenone as indicators, and are obtained by removing water with metal sodium and distilling.
7. The method for preparing aluminum trihydride based on recycling of ether solvents according to claim 1, wherein the steps five to seven are performed 2 times in total.
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| US3816606A (en) * | 1962-10-23 | 1974-06-11 | Olin Mathieson | Method for preparing non-solvated aluminum hydride |
| CN1011218B (en) * | 1987-12-23 | 1991-01-16 | 南开大学 | Synthesis of lithium aluminum hydride |
| US9676625B1 (en) * | 2011-11-07 | 2017-06-13 | Ardica Technologies, Inc. | Synthesis of microcrystalline alpha alane |
| US10435297B2 (en) * | 1999-06-16 | 2019-10-08 | Ardica Technologies, Inc. | Crystallization and stabilization in the synthesis of microcrystalline alpha alane |
| WO2005102919A1 (en) * | 2004-04-05 | 2005-11-03 | Alliant Techsystems, Inc. | METHOD FOR THE PRODUCTION OF α-ALANE |
| CN102659080A (en) * | 2012-05-21 | 2012-09-12 | 天津市北斗星精细化工有限公司 | Novel method for preparing lithium aluminum hydride |
| WO2013184615A1 (en) * | 2012-06-05 | 2013-12-12 | Eveready Battery Company, Inc | Method for preparation of an alane-etherate complex and alane |
| CN103056388B (en) * | 2013-01-22 | 2015-07-22 | 西南科技大学 | Method for preparing aluminum nanoparticles coated with dispersion stabilizers by liquid-phase chemical reduction method |
| CN104725189A (en) * | 2014-12-09 | 2015-06-24 | 车荣睿 | Preparation method for lithium aluminum tri-tert butoxyaluminum hydride |
| CN105197891B (en) * | 2015-10-10 | 2017-06-13 | 哈尔滨工业大学 | It is a kind of from AlH3/MgCl2α AlH are extracted in nano-complex3The method of powder |
| CN105366642B (en) * | 2015-12-21 | 2017-11-07 | 哈尔滨工业大学 | A kind of rare earth synthesizes AlH3Method |
| CN105502290A (en) * | 2015-12-25 | 2016-04-20 | 哈尔滨工业大学 | Simple semi-continuous preparation method of aluminum hydride in diethyl ether solution |
| CN106986306B (en) * | 2017-05-27 | 2019-03-29 | 河南纳宇新材料有限公司 | A kind of preparation method of high-purity α-three aluminum hydride |
| CN109970030B (en) * | 2019-04-19 | 2021-02-09 | 湖北航天化学技术研究所 | Synthesis process of alpha-aluminum trihydride |
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