CN116573613B - Method for synthesizing sodium aluminum hydride by using simple substance - Google Patents
Method for synthesizing sodium aluminum hydride by using simple substance Download PDFInfo
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- CN116573613B CN116573613B CN202310864217.6A CN202310864217A CN116573613B CN 116573613 B CN116573613 B CN 116573613B CN 202310864217 A CN202310864217 A CN 202310864217A CN 116573613 B CN116573613 B CN 116573613B
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- -1 sodium aluminum hydride Chemical compound 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 title claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 46
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 41
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 25
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 22
- 229910052786 argon Inorganic materials 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 8
- 239000012280 lithium aluminium hydride Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229910000104 sodium hydride Inorganic materials 0.000 description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- SPRIOUNJHPCKPV-UHFFFAOYSA-N hydridoaluminium Chemical compound [AlH] SPRIOUNJHPCKPV-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing sodium aluminum hydride by using a simple substance, belonging to the technical field of inorganic chemical synthesis. The preparation method comprises the following steps: (1) Mixing metallic aluminum and metallic sodium in a solvent under anhydrous and anaerobic conditions, and mechanically ball-milling; (2) Transferring the materials to a high-pressure reaction kettle with a stirring function, introducing hydrogen, and heating under stirring; (3) removing the solvent after filtering to obtain sodium aluminum hydride. The preparation process is environment-friendly and is convenient for large-scale production. The prepared sodium aluminum hydride is an excellent hydrogen storage medium and high-efficiency reducing agent, and can be widely applied to safe and high-efficiency storage and transportation of hydrogen and chemical synthesis.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical synthesis, and particularly relates to a method for synthesizing sodium aluminum hydride by taking a simple substance as a raw material. The sodium aluminum hydride is mainly used as a hydrogen storage medium or a reducing agent.
Background
With lithium aluminium hydride (LiAlH) 4 ) Typically an alkali metal complex hydride (MAlH) 4 M is an alkali metal) has strong reducibility and is widely used as a reducing agent in organic synthesis reactions. Lithium aluminum hydride was first prepared by Schlesinger as 1947 using LiH and AlCl 3 Obtained by reaction in diethyl ether.
4LiH + AlCl 3 → LiAlH 4 + 4LiCl
However, this reaction requires the use of expensive LiH, and 4 moles of LiH can give 1 mole of LiAlH 4 The synthesis cost is high.
NaAlH 4 Has a structure similar to LiAlH 4 Because of the reduction characteristic of the metal sodium is used for replacing the metal lithium, the cost is greatly reduced. At the same time NaAlH 4 Also an excellent solid hydrogen storage medium, which is applied to the high-efficiency and safe storage and transportation of hydrogen. U.S. patent publication No. US2576311a and U.S. patent publication No. US2900224a react aluminum bromide with sodium hydride in tetrahydrofuran using a process similar to that described previously for Schlesinger. Although NaAlH is synthesized 4 But AlBr 3 And the cost of (2) is also high.
4NaH + AlBr 3 → NaAlH 4 + 4NaBr
Using AlCl 3 The reaction is difficult, the rate is low, and the yield and the purity are not as good as LiAlH 4 . This is because the NaCl crystallites formed during the reaction are not dissolved by tetrahydrofuran, but cover the NaH surface, preventing further reaction.
Chinese patent application CN1051152A uses high activity NaH and AlCl 3 Reaction in tetrahydrofuran at a stoichiometric ratio of 4:1 gives NaAlH 4 Also, 4 moles of alkali metal hydride are converted, and there is a problem in that the synthesis efficiency is not high.
Ashby et al [ Inorg. Chem. 2(3)(1963)499-504]NaH was found to be capable of synthesizing NaAlH with activated metallic Al in tetrahydrofuran at 345 bar and 140℃ 4 . Similar results were obtained at 140 bar and 150℃with elemental Na instead of NaH:
NaH + Al + 3/2H 2 → NaAlH 4
Na + Al + 2H 2 → NaAlH 4
in comparison, the method for directly synthesizing the elements is simple, the utilization rate of alkali metal is high, and Al is used for replacing AlCl 3 Further reducing the cost of raw materials. However, the metal Al used by Ashby is activated by mixing aluminum powder with triethylaluminum (Et 3 Al) was reacted at 140 bar hydrogen pressure and 140℃for 10 hours.
According to the German patent application with publication number DE1136987B, complex aluminum hydride compounds of Na and Li can be prepared in ethers, amines and aliphatic or aromatic hydrocarbons with the corresponding alkali metal hydrides (or alkali metals) at elevated temperatures and very high hydrogen pressures with vigorous stirring, provided that the aluminum metal has to be activated with an aluminum alkyl. U.S. patent publication No. US3138433A discloses the preparation of NaAlH from NaH and Al under hydrogen pressure in tetrahydrofuran using transition metal halides as catalysts 4 Is a method of (2). NaAlH in the sole example of the patent 4 The highest yield of (2) was only 21.8%.
Publication Inorg. Chem. 5 (9) (1966) on pages 1615-1617 reported the use of the same starting materials Na and activated Al in Et in a solvent 3 Na is synthesized by 350 bar hydrogen pressure direct method under Al catalyst 3 AlH 6 The yield was 98%. This process uses an extremely high hydrogen pressure of 350 bar.
Dysova [ Dokl. Akad. Nauk SSSR 215 (1) (1974), pages 256-259 ]]Reported that Na, al and H were used without using any organic solvent 2 Preparing NaAlH at 280 ℃ under the hydrogen pressure of Na in a molten state and not lower than 175 bar 4 . The main disadvantages of this approach are: the reaction temperature and pressure used are high.
In summary, as the method for synthesizing sodium aluminum hydride in the prior art, there is generally a first method that has too high cost of raw materials and manufacturing cost, or too much byproducts and low yield of sodium aluminum hydride, which is not suitable for industrialization; secondly, the reaction temperature and pressure are too high, which results in large equipment investment, high process energy consumption and poor safety.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing sodium aluminum hydride by using simple substances, wherein sodium aluminum hydride can be obtained under mild conditions after simple mechanical activation treatment of metal sodium and metal aluminum, and the preparation process is environment-friendly and convenient for large-scale production.
The invention is realized by the following technical scheme:
the method for synthesizing sodium aluminum hydride by using simple substance comprises the following steps:
the first step: mechanically mixing metallic aluminum and metallic sodium in a solvent;
and a second step of: transferring the mechanically mixed materials into an autoclave, introducing hydrogen, sealing and heating to obtain sodium aluminum hydride solution or suspension;
and a third step of: the solvent was removed by filtration to give sodium aluminum hydride powder.
Preferably, in the first step, the mechanical mixing means that the materials are mixed with grinding balls in a ball mill tank at normal temperature and normal pressure through rotary extrusion grinding.
Preferably, the temperature range of the heating in the second step is 90-140 ℃; the solvent may be supplemented in the second step.
Preferably, the autoclave in the second step has a pressure in the range of 5 to 8 MPa.
The solvent is one or more than two of ether organic matters capable of dissolving sodium aluminum hydride and is obtained by mixing the two or more than two of the ether organic matters according to any proportion.
Further preferably, the solvent is one or a mixture of two or more of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether in an arbitrary ratio.
Preferably, a catalyst is added in the first step or the second step.
Further preferably, the catalyst is a mixture of any one or more of a transition metal halide and a rare earth metal halide in any proportion.
Still more preferably, the transition metal and the rare earth metal are selected from any one of Ti, zr, sc, hf and Ce.
The catalyst can also be prepared by the following method: adding transition metal halide or rare earth metal halide into fragmented metal sodium, adding the solvent, ball milling to obtain suspension, and removing the solvent to obtain the catalyst.
The invention has the positive effects that:
firstly, the method can be used for preparing high-purity sodium aluminum hydride under the conditions of 90-140 ℃ and 5-8 MPa hydrogen pressure, the process is simple, the high-temperature and high-pressure process conditions of the traditional melting method are avoided, the safety is high, and the energy consumption and the equipment cost are low;
secondly, in the invention, the ball milling treatment adopts a liquid medium, so that not only is agglomeration caused by dry grinding of aluminum powder avoided, but also the aluminum powder and sodium block are effectively mixed, and the reaction is promoted;
thirdly, in the optimization technical scheme of the invention, the reaction conversion rate is greatly improved by using the catalyst;
fourthly, the product sodium aluminum hydride is dissolved in a solvent, the catalyst is a precipitate, and the catalyst is removed by simple filtration, so that the separation process of the product and the catalyst is simplified, and the method is suitable for process amplification and large-scale production of high-performance hydrogen storage materials and reducing agents.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sodium aluminum hydride product prepared in accordance with example one of the present invention.
FIG. 2 is a graph showing the temperature programmed release of hydrogen from sodium aluminum hydride product prepared in example four of the present invention.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
2.7 g aluminum powder and 2.3 g metal sodium were mixed in an argon glove box in a stainless steel ball mill tank (molar ratio 1:1), and 20 ml tetrahydrofuran was added and ball milled at a ball-to-charge ratio of 30:1 for 15 hours, the stainless steel balls were milledThe environment in the tank is normal temperature and normal pressure. Then, the ball-milled mixture was transferred to a stirred autoclave, and 15. 15 ml tetrahydrofuran was added thereto, followed by reaction for 20 hours under stirring at 120℃and 800rpm under a hydrogen pressure of 6.4 MPa. Cooling to remove solvent to obtain Al and Na 3 AlH 6 And NaAlH 4 And (3) a mixture. Transferring the mixture 1.6. 1.6 g to a pressure kettle, adding 20 ml tetrahydrofuran, introducing 8 MPa hydrogen, stirring at 135 ℃ for reaction for 5 hours, and filtering to remove the solvent to obtain 1.73. 1.73 g pure NaAlH 4 . The yield was 32%.
As can be seen from FIG. 1, the obtained product was mixed with NaAlH 4 The diffraction peaks are identical for the standard card (card number PDF # 85-0374).
Example two
2.7 g aluminum powder and 2.51 g sodium metal cut into small pieces were mixed (molar ratio 1:1.09) in an argon glove box, placed in a stainless steel ball mill pot, and 0.74g CeCl was added 3 Then 22 ml tetrahydrofuran is added, and the ball-to-material ratio is 30: ball milling for 40 hours. Then, the ball-milled mixture was transferred to an autoclave and 6.2 MPa hydrogen gas was introduced, and stirred at 100℃and 800rpm for 20 hours, and the pressure was reduced to 2.3 MPa. Supplementing air to 6 MPa, continuing to react for 20 hours, and cooling to room temperature and then keeping the pressure in the kettle at 4.3 MPa. Filtering the solvent to obtain a final product NaAlH of 1.6 g 4 The yield was 30%.
Example III
2.7 g aluminum powder and 2.58 g sodium metal cut into small pieces were mixed (molar ratio 1:1.12) in an argon glove box, placed in a stainless steel ball mill pot, and 0.57g TiCl was added 4 And 30ml of tetrahydrofuran, in a ball-to-charge ratio of 30:1, adding stainless steel balls, ball milling for 20 hours, and transferring into an autoclave. 15. 15 ml tetrahydrofuran was added to the mixture, 6.5MPa hydrogen was introduced, and the mixture was maintained at 95℃and 800rpm for 20 hours. The solvent was removed by filtration to give 2.5 g of NaAlH 4 The yield was 46%.
Example IV
The catalyst is prepared in advance: 1.5 ml TiCl was introduced into the argon glove box 4 Adding into 2.0. 2.0 g chopped metal sodium TiCl 4 50 ml tetrahydrofuran is added into the mixture according to the molar ratio of metal sodium of 1:6, and the ball-to-material ratio of the mixture is 36: ball milling for 10 hours at room temperature to obtain blackA suspension. The pre-prepared Ti-catalyst is obtained after the solvent is removed.
Preparation of sodium aluminum hydride: 2.7 g aluminum powder and 2.3 g metal sodium are mixed (sodium is cut into small pieces) in an argon glove box (molar ratio 1:1), added into a stainless steel ball mill pot, and 0.1g (2% of total mass of aluminum powder and metal sodium) of a pre-prepared catalyst and 30ml tetrahydrofuran are added according to a ball-to-charge ratio of 20: ball milling for 10 hours. Transferring the ball-milling mixture to a pressure kettle, adding 9 ml tetrahydrofuran, introducing 5.2 MPa hydrogen, heating to 120 ℃ under stirring at 800rpm, maintaining for 5 hours, and reducing the pressure to 4 MPa; supplementing hydrogen to 6 MPa, maintaining the temperature at 120 ℃ for 20 hours, and cooling to room temperature to obtain black suspension. Filtering to remove precipitate, removing solvent from the filtrate, and drying to obtain 4.0. 4.0 g off-white solid sodium aluminum hydride. The yield was 74%.
As can be seen from FIG. 2, the total hydrogen evolution of the product obtained, which was programmed to 500℃was 7.4. 7.4 wt%, compared to NaAlH 4 The theoretical hydrogen content is consistent.
Under the condition of other unchanged conditions, zrCl is respectively used 2 HfCl 4 Replacing TiCl 4 The Zr-catalyst prepared in advance and the Hf-catalyst prepared in advance were obtained, and 2% by mass of the Zr-catalyst and 2% by mass of the Hf-catalyst were used, respectively, based on the total mass of the aluminum powder and the sodium metal, to obtain an off-white solid sodium aluminum hydride, the yields were 75% and 66%, respectively.
Example five
2.7 g aluminum powder and 2.3 g metal sodium were mixed (sodium cut into small pieces) in an argon glove box (molar ratio 1:1), added to a stainless steel ball mill pot, 0.35g (7% of total mass of aluminum powder and metal sodium) of the Ti-catalyst prepared in advance of example four and 30ml tetrahydrofuran were added in a ball-feed ratio of 30: ball milling for 10 hours.
The ball-milled mixture was transferred to an autoclave, and then 9 ml tetrahydrofuran was added thereto, and 6 MPa hydrogen was introduced thereto, and reacted at 120℃and 800rpm for 20 hours to obtain a black suspension. The precipitate was removed by filtration, and the filtrate was dried with solvent removal to give sodium aluminum hydride as an off-white solid in 3.4. 3.4 g in 63% yield.
Example six
The catalyst is prepared in advance: scCl was taken up in an argon glove box 3 Adding into fragmented metal sodium, scCl 3 50 ml tetrahydrofuran is added into the mixture according to the molar ratio of metal sodium of 1:6, and the ball-to-material ratio of the mixture is 36: ball milling for 10 hours at room temperature to obtain black suspension. The solvent is removed to obtain the pre-prepared Sc-catalyst.
2.7 g aluminum powder and 2.3 g metal sodium (sodium cut into small pieces) were mixed in an argon glove box (molar ratio 1:1), mixed in a stainless steel ball mill, 30ml diethylene glycol dimethyl ether was added, at a ball-to-material ratio of 30: ball milling for 10 hours.
The ball-milled mixture was transferred to an autoclave, to which 0.25g (5% of the total mass of aluminum powder and sodium metal) of a previously prepared Sc-catalyst was added, and 6.5MPa hydrogen was introduced, and reacted at 140℃and 800rpm for 15 hours. The precipitate was removed by filtration, and the filtrate was freed from solvent under reduced pressure using a rotary evaporator to give sodium aluminum hydride as an off-white solid of 3.8. 3.8 g in 70% yield.
Example seven
The catalyst is prepared in advance: scCl was taken up in an argon glove box 3 Adding into fragmented metal sodium, scCl 3 50 ml triethylene glycol dimethyl ether is added into the mixture according to the molar ratio of metal sodium to metal sodium of 1:6, and the ball material ratio of the mixture is 36: ball milling for 10 hours at room temperature to obtain black suspension. The solvent is removed to obtain the pre-prepared Sc-catalyst.
2.7 g aluminum powder and 2.3 g metal sodium are mixed (sodium is cut into small pieces) in an argon glove box (molar ratio 1:1), mixed in a stainless steel ball mill pot, 30ml triethylene glycol dimethyl ether is added, and the ball-to-material ratio is 30: ball milling for 10 hours.
The ball-milled mixture was transferred to an autoclave, to which 0.25g (5% of the total mass of aluminum powder and sodium metal) of a previously prepared Sc-catalyst was added, and 6.5MPa hydrogen was introduced, and reacted at 140℃and 800rpm for 15 hours. The precipitate was removed by filtration, and the filtrate was freed from solvent under reduced pressure using a rotary evaporator to give sodium aluminum hydride as an off-white solid of 3.9. 3.9 g in 72% yield.
Example eight
The catalyst is prepared in advance: ceCl was placed in an argon glove box 3 Adding into fragmented metal sodium, ceCl 3 Adding 50 ml diethylene glycol di (with a molar ratio of 1:6 to metal sodium)Methyl ether, according to the ball-to-material ratio 36: ball milling for 10 hours at room temperature to obtain black suspension. The pre-prepared Ce-catalyst is obtained after the solvent is removed.
2.7 g aluminum powder and 2.3 g metal sodium were mixed (sodium was cut into small pieces) in an argon glove box (molar ratio 1:1), added to a stainless steel ball mill pot, 0.25g (5% of total mass of aluminum powder and metal sodium) of a previously prepared Ce-catalyst and 30ml tetrahydrofuran were added, in a ball-feed ratio of 30: ball milling for 10 hours.
The ball-milled mixture was transferred to an autoclave, and 7.5 MPa hydrogen was introduced and reacted at 140℃and 800rpm for 20 hours to obtain a black suspension. Filtering to remove precipitate, removing solvent from the filtrate, and drying. 3.0. 3.0 g off-white solid sodium aluminum hydride was obtained in 56% yield.
Example nine
The catalyst is prepared in advance: ceCl was placed in an argon glove box 3 Adding into fragmented metal sodium, ceCl 3 50 ml triethylene glycol dimethyl ether is added into the mixture according to the molar ratio of metal sodium to metal sodium of 1:6, and the ball material ratio of the mixture is 36: ball milling for 10 hours at room temperature to obtain black suspension. The pre-prepared Ce-catalyst is obtained after the solvent is removed.
2.7 g aluminum powder and 2.3 g metal sodium were mixed (sodium was cut into small pieces) in an argon glove box (molar ratio 1:1), added to a stainless steel ball mill pot, 0.25g (5% of total mass of aluminum powder and metal sodium) of a previously prepared Ce-catalyst and 30ml triethylene glycol dimethyl ether were added in a ball-feed ratio of 30: ball milling for 10 hours.
The ball-milled mixture was transferred to an autoclave, and 7.5 MPa hydrogen was introduced and reacted at 140℃and 800rpm for 20 hours to obtain a black suspension. Filtering to remove precipitate, removing solvent from the filtrate, and drying. 3.7. 3.7 g off-white solid sodium aluminum hydride was obtained in 69% yield.
Claims (7)
1. The method for synthesizing sodium aluminum hydride by using simple substance is characterized by comprising the following steps:
the first step: mechanically mixing metallic aluminum and metallic sodium in a solvent; the solvent is one or more than two of ether organic matters capable of dissolving sodium aluminum hydride and is obtained by mixing according to any proportion;
and a second step of: transferring the mechanically mixed materials into an autoclave, introducing hydrogen, sealing and heating to obtain sodium aluminum hydride solution or suspension; the heating temperature range is 90-140 ℃; in this step, the solvent is supplemented; the pressure range of the autoclave is 5-8 MPa;
and a third step of: filtering, and removing the solvent from the filtrate to obtain powdery sodium aluminum hydride;
the catalyst is added in the first step or the second step; the catalyst is one or more than two of transition metal halide and rare earth metal halide mixed according to any proportion.
2. The method for synthesizing sodium aluminum hydride by using a simple substance as claimed in claim 1, wherein: the mechanical mixing in the first step means that the materials are mixed with grinding balls in a ball milling tank at normal temperature and normal pressure through rotary extrusion grinding.
3. The method for synthesizing sodium aluminum hydride by using a simple substance as claimed in claim 1, wherein: the solvent is one or more than two of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether which are mixed according to any proportion.
4. The method for synthesizing sodium aluminum hydride by using a simple substance as claimed in claim 1, wherein: the transition metal and the rare earth metal are selected from any one of Ti, zr, sc, hf and Ce.
5. The method for synthesizing sodium aluminum hydride by using simple substance is characterized by comprising the following steps:
the first step: mechanically mixing metallic aluminum and metallic sodium in a solvent; the solvent is one or more than two of ether organic matters capable of dissolving sodium aluminum hydride and is obtained by mixing according to any proportion;
and a second step of: transferring the mechanically mixed materials into an autoclave, introducing hydrogen, sealing and heating to obtain sodium aluminum hydride solution or suspension; the heating temperature range is 90-140 ℃; in this step, the solvent is supplemented; the pressure range of the autoclave is 5-8 MPa;
and a third step of: filtering, and removing the solvent from the filtrate to obtain powdery sodium aluminum hydride;
the catalyst is added in the first step or the second step; adding transition metal halide or rare earth metal halide into fragmented metal sodium, adding the solvent, ball milling to obtain suspension, and removing the solvent to obtain the catalyst.
6. The method for synthesizing sodium aluminum hydride by using a simple substance as claimed in claim 5, wherein: the mechanical mixing in the first step means that the materials are mixed with grinding balls in a ball milling tank at normal temperature and normal pressure through rotary extrusion grinding.
7. The method for synthesizing sodium aluminum hydride by using a simple substance as claimed in claim 5, wherein: the solvent is one or more than two of tetrahydrofuran, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether which are mixed according to any proportion.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1273454A (en) * | 1959-09-02 | 1961-10-13 | Hercules Powder Co Ltd | Process for the preparation of alkali metal aluminum hydride |
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
| EP2689844A1 (en) * | 2007-09-21 | 2014-01-29 | MEMC Electronic Materials, Inc. | Catalysts for purification of silicon tetrafluoride |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1273454A (en) * | 1959-09-02 | 1961-10-13 | Hercules Powder Co Ltd | Process for the preparation of alkali metal aluminum hydride |
| EP2689844A1 (en) * | 2007-09-21 | 2014-01-29 | MEMC Electronic Materials, Inc. | Catalysts for purification of silicon tetrafluoride |
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
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