CN115744817A - Wide-temperature alcoholysis rapid hydrogen production method - Google Patents
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 134
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 134
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 56
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 62
- 239000000956 alloy Substances 0.000 claims abstract description 62
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910019064 Mg-Si Inorganic materials 0.000 claims abstract description 12
- 229910019406 Mg—Si Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910014106 Na-Si Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
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- 239000012300 argon atmosphere Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011863 silicon-based powder Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910019443 NaSi Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- -1 water Chemical compound 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of hydrogen production, and particularly discloses a method for rapidly producing hydrogen by wide-temperature alcoholysis. The invention adopts silicon-based alloy which is easy to prepare and methanol as reaction raw materials, and the alcoholysis reaction is carried out by utilizing the direct contact of the silicon-based alloy and the methanol, so that a large amount of hydrogen can be quickly obtained. The silicon-based alloy includes Li-Si alloy, na-Si alloy and Mg-Si alloy; the solid-liquid reaction hydrogen production process is carried out under the wide temperature condition of minus 40 to 50 ℃. The method has the advantages of simple operation, wide hydrogen supply temperature range, high hydrogen production amount, environmental protection, easy industrial production and the like, can quickly produce hydrogen below 0 ℃, is suitable for on-site hydrogen supply according to needs under multiple working conditions and complex extreme environments, and is safe and reliable.
Description
Technical Field
The invention relates to the technical field of hydrogen production, in particular to a method for rapidly producing hydrogen by wide-temperature alcoholysis.
Background
The hydrogen is used as a green energy carrier, has the advantages of being renewable, high in energy density, zero in emission and the like, and is regarded as an important means for realizing carbon emission reduction. However, efficient and safe storage and transportation of hydrogen still limits the large-scale application of hydrogen energy. Compared with the traditional high-pressure hydrogen storage technology, the hydrogen production technology based on the chemical reaction between the solid reducing agent and the liquid hydrogen source (such as water, methanol and the like) can realize the storage, transportation and supply of hydrogen at normal temperature and normal pressure, not only meets the operation requirement of a hydrogen supply system, but also avoids the safety problem of high-pressure hydrogen storage and transportation.
The solid reducing agent commonly used in the chemical reaction hydrogen production technology mainly comprises Mg, al, si and NaBH 4 For example, xu et al prepared a silicon-based hydrogen production material by ball milling Si powder, KOH and sucrose, which material spontaneously reacts with water to generate a large amount of hydrogen gas at temperatures above 19 ℃ (International Journal of hydrogen Energy,2016, 41, 12730-12737). However, the diversity of global hydrogen environments requires that hydrogen supply systems can supply hydrogen rapidly even at temperatures below 0 ℃, but pure water cannot be used for hydrogen production under these conditions due to freezing point (0 ℃). For example, the company SiGNa chemical in the united states developed an ionic NaSi compound hydrolysis hydrogen supply system which is excellent in hydrogen production performance under room temperature conditions, but fails to satisfy effective hydrogen supply under the condition below 0 ℃ (US 9669371b2.
At present, in order to take account of hydrogen environment below 0 ℃, a reactant with a lower freezing point, such as a water/ethanol mixed solution, a high-concentration salt solution and the like, is generally adopted for chemical reaction hydrogen production. Wherein Mussabek et al prepares a porous nano-silicon powder by using a complex HF electrochemical etching technology, the porous nano-silicon powder reacts with a water/ethanol mixed solution for 100 hours at 23 ℃ to release 820mL/g of hydrogen, but the reaction is carried out for more than 120 hours at-40 ℃ to release 343mL/g of hydrogen (Nanomaterials, 2020, 10, 1413); su et Al prepared an Al alloy/NaCl/g-C by mechanical ball milling 3 N 4 A composite material which releases 1170mL/g of hydrogen in 1min at 25 ℃ in combination with tap water, but which releases 1006mL/g of hydrogen only after reacting with 23wt% NaCl solution for 60min at-20 ℃ (Energy, 2021, 218, 119498).
In addition, through CaMg 2 The alcoholysis reaction between the alloy and methanol is carried out, and the same is trueHydrogen production (ChemSusChem, 2020, 13, 2709-2718) was achieved, 858mL/g of hydrogen being liberated in 1min at 25 ℃ but only 563mL/g of hydrogen being liberated over 100min at-20 ℃. Obviously, although the above method can realize effective supply of hydrogen at room temperature, the hydrogen production rate under low temperature condition is very slow, and cannot meet the requirement of rapid hydrogen supply in low temperature environment.
Therefore, how to provide a method for rapidly producing hydrogen by wide-temperature alcoholysis, which realizes low-temperature rapid hydrogen production on the basis of ensuring low raw material price, high hydrogen production amount and wide hydrogen supply temperature range, is a difficult problem to be solved urgently in the field.
Disclosure of Invention
In view of the above, the invention provides a wide-temperature alcoholysis rapid hydrogen production method, so as to solve the problems that the existing hydrogen production method is slow in hydrogen production rate under a low-temperature condition and is difficult to meet the application requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
a wide-temperature alcoholysis rapid hydrogen production method comprises the following steps: carrying out alcoholysis reaction on the silicon-based alloy and methanol to obtain hydrogen;
the mass volume ratio of the silicon-based alloy to the methanol is 0.2-1.2 g:5mL.
Preferably, the temperature of the alcoholysis reaction is-40 to 50 ℃, and the time of the alcoholysis reaction is 0.1 to 23min.
Preferably, the silicon-based alloy comprises one or more of Li-Si alloy, na-Si alloy and Mg-Si alloy.
Preferably, the atomic number ratio of Li to Si in the Li-Si alloy is 12 to 22:5 to 7; the Na-Si alloy has an atomic number ratio of Na to Si of 1 to 4:1 to 23; the atomic number ratio of Mg to Si in the Mg-Si alloy is 2:1.
preferably, the particle size of the Mg-Si alloy is 1 to 10 μm.
Preferably, the volume concentration of water in the methanol is less than or equal to 0.5 percent.
Preferably, the alcoholysis reaction is carried out under a protective atmosphere.
Preferably, the protective atmosphere includes one or more of a nitrogen atmosphere and a rare gas atmosphere.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the hydrogen production method has wide hydrogen supply temperature range, can realize hydrogen supply at the temperature of between 40 ℃ below zero and 50 ℃, meets the field hydrogen supply requirements of most outdoor working conditions and even extreme low-temperature environments, and has high safety.
2. The hydrogen production method has high hydrogen supply rate and can realize controllable and rapid hydrogen production in a wide temperature range.
3. The hydrogen production method adopts the silicon-based solid reducing agent, wherein silicon completely participates in hydrogen production reaction, and the outermost layer of the silicon has 4 electrons, so that the hydrogen production amount is higher than that of reducing agents such as Mg, al and the like.
4. The hydrogen production reaction has low corrosion of byproducts, low requirement on a reaction container, easy separation, recovery and reuse and high economy.
5. The hydrogen prepared by the method has high purity, meets the requirements of hydrogen end such as fuel cell, hydrogen internal combustion engine and the like on the purity of the hydrogen, and can be directly used by the hydrogen end.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a kinetic plot of hydrogen production by alcoholysis of Li-Si alloys of examples 1 to 4, wherein a corresponds to example 1, b corresponds to example 2, c corresponds to example 3, and d corresponds to example 4;
FIG. 2 is a kinetic plot of alcoholysis hydrogen production from the NaSi alloy of example 5;
FIG. 3 is Mg of example 6 2 A kinetic curve of alcoholysis hydrogen production of Si alloy;
FIG. 4 is Mg of example 14 2 A kinetic curve of alcoholysis hydrogen production of Si alloy under different low temperature conditions;
FIG. 5 shows Li in example 15 22 Si 5 The kinetic curve of alcoholysis hydrogen production of the alloy under different low temperature conditions.
Detailed Description
The invention provides a wide-temperature alcoholysis rapid hydrogen production method, which comprises the following steps: carrying out alcoholysis reaction on the silicon-based alloy and methanol to obtain hydrogen;
the mass volume ratio of the silicon-based alloy to the methanol is 0.2-1.2 g:5mL, preferably 0.5 to 1g:5mL, more preferably 0.7 to 0.9g:5mL, and further preferably 0.8g:5mL.
In the invention, the temperature of the alcoholysis reaction is-40 to 50 ℃, preferably-40 to 5 ℃, further preferably-40 to 0 ℃, and further preferably-40 to-5 ℃; the temperature of the alcoholysis reaction can be specifically-35 ℃, 30 ℃, 25 ℃,20 ℃, 10 ℃,20 ℃, 30 ℃ and 40 ℃.
In the present invention, the time of the alcoholysis reaction is 0.1 to 23min, and specifically may be 0.1min,0.5min, 1min, 2min, 4min, 5min, 6min, 8min, 10min, or 12min.
In the invention, the silicon-based alloy comprises one or more of Li-Si alloy, na-Si alloy and Mg-Si alloy.
In the present invention, the atomic number ratio of Li to Si in the Li-Si alloy is 12 to 22:5 to 7, preferably 14 to 20:5 to 7, more preferably 15 to 18:6, and more preferably 16:6; the atomic number ratio of Na to Si in the Na-Si alloy is 1-4: 1 to 23, preferably 2 to 3:2 to 20, more preferably 2:5 to 15, and preferably 2:10; the atomic number ratio of Mg to Si in the Mg-Si alloy is 2:1.
in the present invention, the particle diameter of the Mg-Si alloy is 1 to 10 μm, and specifically 2 μm, 4 μm, 5 μm, 6 μm, or 8 μm.
In the present invention, the particle diameters of the Li-Si alloy and the Na-Si alloy are not particularly required.
In the invention, the Mg-Si alloy with the particle size of 1-10 μm is preferably obtained by ball milling large-particle Mg-Si alloy, the ball milling atmosphere is non-oxidizing atmosphere, and is preferably one or more of nitrogen atmosphere and rare gas atmosphere, and the rare gas atmosphere comprises one or more of helium, neon and argon.
In the present invention, the ball-milling preferably has a ball-to-material ratio of 10 to 30:1, specifically 12: 1. 15: 1. 18: 1. 20: 1. 25:1; the ball milling time is preferably 0.1-2 h, and specifically can be 0.5h, 1h and 1.5h; the ball-milling rotation speed is preferably 200 to 500rpm, and specifically may be 250rpm, 300rpm, 350rpm, 400rpm or 450rpm.
In the present invention, ball milling also enables Mg 2 The Si alloy generates fresh surface and microscopic defects, which is beneficial to improving the generation of hydrogen.
In the present invention, the volume concentration of the impurity in the methanol, i.e., water, is not more than 0.5%, and specifically may be 0.4%, 0.3%, 0.2%, 0.1%, 0.05%, 0%.
In the present invention, the alcoholysis reaction is carried out under a protective atmosphere.
In the present invention, the protective atmosphere includes one or more of a nitrogen atmosphere and a rare gas atmosphere.
In the present invention, the pressure of the alcoholysis reaction is preferably normal atmospheric pressure.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Under the argon atmosphere of 0.1MPa, 0.2g of Li is weighed 22 Si 5 The alloy is put into a 10mL double-opening reaction tube, the temperature is kept at 25 ℃, 5mL of methanol at 25 ℃ is injected, the reaction is finished after 0.6min at 25 ℃, and 1739mL/g of hydrogen is released (mL/g represents the corresponding hydrogen production per gram of alloy). Kinetics of alcoholysis Hydrogen production for this exampleThe curve is shown in FIG. 1a, and it can be seen from FIG. 1a that Li 22 Si 5 The alcoholysis hydrogen production performance of the alloy is excellent.
Example 2
Under the argon atmosphere of 0.1MPa, 0.2g of Li is weighed 13 Si 4 The alloy was put into a 10mL double-port reaction tube, and 5mL of 25 ℃ methanol was injected while maintaining the temperature at 25 ℃, and after 0.7min at 25 ℃, the reaction was completed and 1616mL/g of hydrogen was released. The kinetic curve for hydrogen production by alcoholysis in this example is shown in FIG. 1b, and Li is shown in FIG. 1b 13 Si 4 The alcoholysis hydrogen production performance of the alloy is excellent.
Example 3
Under the argon atmosphere of 0.1MPa, 0.2g of Li is weighed 7 Si 3 The alloy was charged into a 10mL double-port reaction tube, the temperature was kept at 25 ℃, 5mL of 25 ℃ methanol was injected, and the reaction was completed after 1min at 25 ℃ with release of 944mL/g hydrogen. The kinetic curve for hydrogen production by alcoholysis in this example is shown in FIG. 1c, and Li is shown in FIG. 1c 7 Si 3 The alcoholysis hydrogen production performance of the alloy is excellent.
Example 4
Under the argon atmosphere of 0.1MPa, 0.2g of Li is weighed 12 Si 7 The alloy was put into a 10mL double-port reaction tube, the temperature was kept at 25 ℃, 5mL of 25 ℃ methanol was injected, and the reaction was completed after 1min at 25 ℃ with the release of 820mL/g hydrogen. The kinetic curve for hydrogen production by alcoholysis in this example is shown in FIG. 1d, from which it can be seen that Li in FIG. 1d 12 Si 7 The alcoholysis hydrogen production performance of the alloy is excellent.
Example 5
Under the argon atmosphere of 0.1MPa, 0.2g of NaSi alloy is weighed and put into a 10mL double-opening reaction tube, the temperature is kept at 25 ℃, 5mL of methanol at 25 ℃ is injected, the reaction is finished after 0.3min under the condition of 25 ℃, and 1144mL/g of hydrogen is released. The kinetic curve of alcoholysis hydrogen production in this example is shown in fig. 2, and it can be seen from fig. 2 that the alcoholysis hydrogen production performance of the NaSi alloy is excellent.
Example 6
Under the argon atmosphere of 0.1MPa, the ratio of balls to materials is 30:1 weighing stainless steel ball and Mg 2 Adding Si into a ball milling tankThen placing the ball milling tank on a planetary ball mill, adjusting the rotating speed to 400rpm, and carrying out ball milling for 2 hours in an argon atmosphere to obtain Mg with the particle size of 1-2 mu m 2 And (3) Si powder.
Under the argon atmosphere of 0.1MPa, 0.2g of ball-milled Mg is weighed 2 The Si powder was put into a 10mL double-port reaction tube, the temperature was kept at 25 ℃, 5mL of 25 ℃ methanol was injected, and after 0.2min at 25 ℃, the reaction was completed and 1145mL/g hydrogen gas was released. The kinetic curve of alcoholysis hydrogen production in this example is shown in FIG. 3. From FIG. 3, it can be seen that Mg 2 The alcoholysis hydrogen production performance of the Si alloy is excellent.
Example 7
Under the argon atmosphere of 0.1MPa, the ratio of pellets to material is 10:1 weighing stainless steel balls and Mg 2 Adding Si into a ball milling tank, placing the ball milling tank on a planetary ball mill, adjusting the rotating speed to 300rpm, and performing ball milling for 1.5 hours in an argon atmosphere to obtain Mg with the particle size of 4-10 mu m 2 And (3) Si powder.
Under the argon atmosphere of 0.1MPa, 0.8g of ball-milled Mg is weighed 2 The Si alloy is put into a 10mL double-opening reaction tube, the temperature is kept at 25 ℃, 5mL of methanol with the temperature of 25 ℃ is injected, the reaction can be finished after 1min at the temperature of 25 ℃, and 1134mL/g of hydrogen is released.
Example 8
Under 0.1MPa argon atmosphere, according to a ball-to-feed ratio of 25:1 weighing stainless steel balls and Mg 2 Adding Si into a ball milling tank, placing the ball milling tank on a planetary ball mill, adjusting the rotating speed to 400rpm, and performing ball milling for 1h in an argon atmosphere to obtain Mg with the particle size of 2-4 mu m 2 And (3) Si powder.
Under the argon atmosphere of 0.1MPa, 0.5g of ball-milled Mg is weighed 2 The Si alloy is put into a 10mL double-opening reaction tube, the temperature is kept at 25 ℃, 5mL of methanol with the temperature of 25 ℃ is injected, the reaction can be finished after 1min at the temperature of 25 ℃, and 1140mL/g of hydrogen is released.
Example 9
This example differs from example 1 only in that the addition and reaction were carried out at 30 deg.C, 20 deg.C and 10 deg.C, respectively. Wherein, at 30 ℃, li 22 Si 5 1742mL/g of hydrogen can be released from the alloy within 0.7 min; at 20 ℃ C，Li 22 Si 5 The alloy can release 1691mL/g hydrogen within 0.9 min; at 10 ℃ Li 22 Si 5 The alloy can release 1656mL/g of hydrogen within 0.9 min.
Example 10
This example differs from example 2 only in that the addition and reaction were carried out at 50 deg.C, 40 deg.C, 30 deg.C and 20 deg.C, respectively. Wherein, at 50 ℃, li 13 Si 4 The alloy can release 1779mL/g of hydrogen within 0.6 min; at 40 ℃ Li 13 Si 4 The alloy can release 1755mL/g hydrogen within 0.9 min; at 30 ℃ Li 13 Si 4 The alloy can release 1622mL/g hydrogen within 1 min; at 20 ℃ Li 13 Si 4 The alloy can release 1593mL/g of hydrogen in 1 min.
Example 11
This example differs from example 3 only in that the addition and reaction are carried out at 50 deg.C, 40 deg.C, 30 deg.C and 20 deg.C, respectively. At 50 deg.C, li 7 Si 3 The alloy can release 1356mL/g of hydrogen within 0.7 min; at 40 ℃ Li 7 Si 3 The alloy can release 1236mL/g of hydrogen within 0.8 min; at 30 ℃ Li 7 Si 3 The alloy can release 1199mL/g of hydrogen within 0.8 min; at 20 ℃ Li 7 Si 3 The alloy can release 930mL/g of hydrogen within 1 min.
Example 12
This example differs from example 4 only in that the addition and reaction were carried out at 50 deg.C, 40 deg.C, 30 deg.C and 20 deg.C, respectively. At 50 ℃ Li 12 Si 7 The alloy can release 1034mL/g of hydrogen within 0.5 min; at 40 ℃ Li 12 Si 7 The alloy can release 956mL/g of hydrogen within 1 min; at 30 ℃ Li 12 Si 7 The alloy can release 867mL/g of hydrogen within 1 min; at 20 ℃ Li 12 Si 7 The alloy can release 815mL/g of hydrogen within 1 min.
Example 13
This example differs from example 6 only in that it proceeds at 10 ℃ and 0 ℃ respectivelyAnd (4) feeding and reacting. Wherein, at 10 ℃, mg 2 The Si alloy can release 1144mL/g of hydrogen within 0.5 min; at 0 ℃ Mg 2 The Si alloy can release 1143mL/g of hydrogen within 0.7 min.
Example 14
This example only differs from example 6 in that the feeding and reaction are carried out at-5 deg.C, -10 deg.C, -15 deg.C, -20 deg.C and-25 deg.C, respectively, with Mg at-5 deg.C 2 The Si alloy can react within 4.3min and release 1100mL/g of hydrogen; mg at-10 deg.C 2 The Si alloy can react within 14.5min and release 1084mL/g hydrogen; mg at-15 deg.C 2 The Si alloy can be reacted within 13min, and 1057mL/g hydrogen is released; mg at-20 deg.C 2 The Si alloy can react within 14.8min and release 1041mL/g of hydrogen; mg at-25 deg.C 2 The Si alloy can be reacted within 14.8min, and 1025mL/g hydrogen is released; the kinetic curve of alcoholysis hydrogen production in this example is shown in FIG. 4. It can be seen from FIG. 4 that Mg of the present invention 2 The low-temperature alcoholysis hydrogen production performance of the Si alloy is excellent.
Example 15
This example differs from example 1 only in that the charging and reaction are carried out at-10 deg.C, -20 deg.C, -30 deg.C and-40 deg.C, respectively, where Li is at-10 deg.C 22 Si 5 The alloy can react within 0.6min and release 1613mL/g of hydrogen; li at-20 DEG C 22 Si 5 The alloy can react within 1.2min and release 1386mL/g hydrogen; li at-30 DEG C 22 Si 5 The alloy can react within 1.8min and release 1254mL/g of hydrogen; li at-40 DEG C 22 Si 5 The alloy can react completely within 23min and release 1091mL/g of hydrogen. The alcoholysis hydrogen production power curve of this example is shown in FIG. 5. It can be seen from FIG. 5 that Li according to the present invention 22 Si 5 The low-temperature alcoholysis hydrogen production performance of the alloy is excellent.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A wide-temperature alcoholysis method for rapidly producing hydrogen is characterized by comprising the following steps: carrying out alcoholysis reaction on the silicon-based alloy and methanol to obtain hydrogen;
the mass volume ratio of the silicon-based alloy to the methanol is 0.2-1.2 g:5mL.
2. The wide-temperature alcoholysis rapid hydrogen production method of claim 1, wherein the temperature of the alcoholysis reaction is-40 to 50 ℃ and the time of the alcoholysis reaction is 0.1 to 23min.
3. A wide temperature alcoholysis fast hydrogen production method as claimed in claim 1 or 2 wherein said silicon based alloy comprises one or more of Li-Si alloy, na-Si alloy and Mg-Si alloy.
4. The wide-temperature alcoholysis rapid hydrogen production method of claim 3, wherein the atomic number ratio of Li to Si in the Li-Si alloy is 12-22: 5 to 7; the Na-Si alloy has an atomic number ratio of Na to Si of 1 to 4:1 to 23; the atomic number ratio of Mg to Si in the Mg-Si alloy is 2:1.
5. the wide-temperature alcoholysis rapid hydrogen production method according to claim 4, wherein the particle size of the Mg-Si alloy is 1-10 μm.
6. A wide temperature alcoholysis process for producing hydrogen rapidly as claimed in claim 1, 2, 4 or 5 wherein the water volume concentration of said methanol is less than or equal to 0.5%.
7. The wide temperature alcoholysis fast hydrogen production method according to claim 6, wherein the alcoholysis reaction is performed under a protective atmosphere.
8. The wide-temperature alcoholysis rapid hydrogen production method according to claim 7, wherein the protective atmosphere comprises one or more of a nitrogen atmosphere and a noble gas atmosphere.
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| CN107585738A (en) * | 2017-07-21 | 2018-01-16 | 华南理工大学 | A kind of Mg Mg2Si composite hydrolysis hydrogen manufacturing materials and preparation method thereof and the method for hydrolytic hydrogen production |
| CN115159453A (en) * | 2022-08-17 | 2022-10-11 | 昆明理工大学 | Method for preparing hydrogen by hydrolyzing photovoltaic cutting silicon waste |
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| CN107585738A (en) * | 2017-07-21 | 2018-01-16 | 华南理工大学 | A kind of Mg Mg2Si composite hydrolysis hydrogen manufacturing materials and preparation method thereof and the method for hydrolytic hydrogen production |
| CN115159453A (en) * | 2022-08-17 | 2022-10-11 | 昆明理工大学 | Method for preparing hydrogen by hydrolyzing photovoltaic cutting silicon waste |
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