CN112850641A - Halogen anion hydrolysis medium greening regulation and control method for magnesium-based alloy hydrolysis hydrogen production - Google Patents
Halogen anion hydrolysis medium greening regulation and control method for magnesium-based alloy hydrolysis hydrogen production Download PDFInfo
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Abstract
The invention discloses a halogen anion hydrolysis medium greening regulation and control method for preparing hydrogen by hydrolyzing magnesium-based alloy, which comprises the following steps of 1, calculating the mass of distilled water/tap water and halogen anions, and weighing by using a balance; step 2, adding the weighed halogen anions into distilled water/tap water to prepare a hydrolysis modified solution, and rapidly stirring the prepared solution; step 3, placing the prepared hydrolysis modification solution on a magnetic stirrer, heating and stirring for 30min, and then placing the solution in a constant-temperature water bath kettle; and 4, placing the magnesium-based alloy in the fully dissolved hydrolysis modified solution for hydrolysis hydrogen production test, collecting hydrogen by adopting a drainage method, recording the mass of the hydrogen at intervals of 5s, and finally performing data processing. The invention optimizes the hydrolysis medium system on the basis of reducing the cost, provides conditions for green hydrolysis hydrogen production of magnesium-based alloy, and effectively improves H2Utilization ratio of O molecules.
Description
Technical Field
The invention relates to the technical field of hydrolytic hydrogen production alloy materials, in particular to a green regulation and control method of a halogen anion hydrolytic medium for preparing hydrogen by hydrolyzing magnesium-based alloy.
Background
In order to respond to the national energy revolution and the policies related to the transformation and upgrading of the automobile industry, the development and utilization of clean, efficient and low-carbon novel hydrogen energy for 'driving' future life is a research subject in China and even the world. A novel movable, convenient and large-scale on-site hydrolysis hydrogen production method is more and more concerned by domestic and foreign scholars in recent years, and the method can immediately produce hydrogen through rapid hydrolysis reaction. Compared with ideal hydrogen production modes such as photocatalysis and electrocatalysis, the on-site hydrolysis hydrogen production is considered to be an effective transition large-scale hydrogen production mode. In some special occasions (such as the field, remote areas or mountainous areas, etc.), large-scale hydrogen provided by field hydrolysis can be used as power fuel and a fuel cell power generation system, and the storage link of the hydrogen is effectively avoided. The magnesium-based material can react with water to generate a large amount of hydrogen, and at present, a field hydrolysis hydrogen production mode using high-activity magnesium-based alloy as a medium has high hydrogen production capacity, is safe and reliable, and becomes a research hotspot. However, the hydrogen production by hydrolysis of the magnesium-based alloy has long reaction period, complex process and high costAnd the problem of environmental pollution is increased to a certain extent, so that the wide application of the magnesium-based hydrogen production alloy by hydrolysis is limited. In addition, because of MgO passivation layer on the surface of the magnesium-based alloy and colloid Mg (OH) formed in the process of hydrogen production through hydrolysis2The membrane wraps unhydrolyzed metal particles, so that medium transmission is hindered, and initial kinetics of hydrogen production by hydrolysis and hydrogen production yield are reduced. The diffusion channel is added, the mass transfer path is shortened, the medium transmission is accelerated, and the method is an important means for improving the hydrolysis hydrogen production kinetics and the final hydrogen production capacity of the magnesium-based alloy. Therefore, people pay more and more attention to the green modification strategy for researching the magnesium-based alloy under the low-temperature condition, and the magnesium-based alloy is rapid, low in cost and low in energy consumption.
At present, the regulation and control method of magnesium-based hydrolysis hydrogen production alloy mainly comprises two aspects, namely the modification of the magnesium-based alloy and the regulation and control of hydrolysis hydrogen production medium. As for the alloy itself, the electrochemical activity of the magnesium-based hydrogen-producing hydrolytic alloy is adjusted by means of structure refinement, compounding, hydrogenation, surface catalysis and the like, and the method is an effective way for realizing rapid hydrogen production hydrolytic reaction. Although the hydrolysis hydrogen production rate, the final hydrogen production capacity and the hydrolysis hydrogen production thermodynamic are gradually improved, great efforts are still needed to find a green, simple and feasible magnesium-based alloy modification strategy with low material and energy consumption, and a deeper hydrolysis regulation mechanism also draws wide attention.
Besides, another aspect of modification of magnesium-based hydrolyzed hydrogen-producing alloy-hydrolysis medium regulation and control is to introduce acid or alkali into neutral distilled water or tap water to erode the surface passive film (MgO or Mg (OH))2) Quickening the hydrolysis hydrogen production speed, improving the hydrolysis hydrogen production capability and obtaining clean and pollution-free hydrogen. However, the hydrolysis medium modification method increases the hydrolysis hydrogen production cost, has more complex process and higher requirements on hydrogen production equipment, and is difficult to be practically applied. On the other hand, the hydrolysis medium modified ion-pair magnesium-based alloy surface passivation film (MgO or Mg (OH))2) Weak penetration, blocked hydrolysis transmission channel, water molecules unable to contact with fresh alloy continuously, H2The utilization rate of O molecules is extremely low. In view of the above two reasons, a green water dissociation molecule regulation method is sought to improve magnesium baseThe hydrogen production performance of alloy hydrolysis is the key point of future research.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a halogen anion hydrolysis medium green regulation and control method for magnesium-based alloy hydrolysis hydrogen production, which optimizes a hydrolysis medium system on the basis of reducing the cost, provides conditions for green hydrolysis hydrogen production of magnesium-based alloy, and effectively improves H content2Utilization ratio of O molecules.
In order to achieve the purpose, the invention adopts the technical scheme that:
a halogen anion hydrolysis medium greening regulation and control method for magnesium-based alloy hydrolysis hydrogen production comprises the following steps;
step 1, weighing
The amount of the halogen anion substance was 0.1mol, and the mass of the distilled water/tap water and the halogen anion was calculated by the formulas n ═ M/M and c ═ (a/B) × 100% (n is the amount of the substance, M is the molar mass of the substance, M is the mass of the substance, c is the concentration of the solution, a is the mass of the solute, and B is the mass of the solution), and weighed with a balance;
step 2, preparing a solution
Adding the weighed halogen anions into distilled water/tap water to prepare a hydrolysis modified solution with the concentration of 2-5%, and quickly stirring the prepared solution;
step 3, dissolving
In order to fully dissolve the halogen anions in distilled water/tap water, the prepared hydrolysis modified solution is placed on a magnetic stirrer, heated and stirred for 30min and then placed in a constant-temperature (293-323K) water bath kettle;
step 4, hydrolysis hydrogen production
And (3) putting 1g of magnesium-based alloy into the fully dissolved hydrolysis modified solution with the concentration of 2-5% for hydrolysis hydrogen production test, collecting hydrogen by adopting a drainage method, recording the mass of the hydrogen at intervals of 5s, and finally performing data processing.
The hydrolysis modification solution has a concentration of 2-5%, and the solution is distilled water/tap water + M (M ═ NaF, NaCl, NaBr, NaI), wherein the amount of M is 0.1 mol.
The invention has the beneficial effects that:
the univalent halogen anion in the hydrolysis medium modification of the invention passivates the surface of the magnesium-based alloy (MgO or Mg (OH))2) The penetration capacity is stronger, the hydrolysis transmission channel is increased, water molecules can continuously contact with the fresh alloy to continuously produce hydrogen, and the H is obviously improved2Utilization ratio of O molecules.
The halogen anion hydrolysis modified solution which is nontoxic, harmless and easy to obtain and is used in the invention can be H2O molecule adsorption dissociation and rapid mass transfer provide low energy barrier sites and convenient channels, thereby rapidly hydrolyzing and producing hydrogen and obviously improving the hydrolytic thermodynamic behavior of the magnesium-based alloy.
The halogen anion is adopted to carry out green regulation and control on the hydrolysis medium, on one hand, the cost and the energy consumption are reduced, on the other hand, the halogen anion solution which is non-toxic and harmless and is easy to obtain is introduced, so that the corrosion problem of equipment and the pollution problem of the environment are avoided.
The magnesium-based alloy and the halogen anion solution can be hydrolyzed to generate hydrogen under the condition of low temperature or room temperature, heating or warming is not needed, the reaction barrier is low, and the energy consumption is reduced.
Drawings
FIG. 1 is a graph of hydrogen production from hydrolysis of magnesium-based alloys in different halogen anion solutions.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A green hydrolysis solution of halogen anion hydrolysis medium for preparing hydrogen by hydrolyzing magnesium-based alloy is a 2-5% seawater modification solution, which is distilled water/tap water + M (M is NaF, NaCl, NaBr and NaI), wherein the amount of M is 0.1 mol. The halogen anion hydrolysis modification solution concentration in this embodiment is 2%.
A greenization regulation and control method of a halogen anion hydrolysis medium for magnesium-based alloy hydrolysis hydrogen production comprises the following steps:
step 1, weighing
The amount of the halogen anion substance was 0.1mol, and the mass of the distilled water/tap water and the halogen anion was calculated by the formulas n ═ M/M and c ═ (a/B) × 100% (n is the amount of the substance, M is the molar mass of the substance, M is the mass of the substance, c is the concentration of the solution, a is the mass of the solute, and B is the mass of the solution), and weighed with a balance.
Step 2, preparing a solution
And adding the weighed halogen anions into distilled water/tap water to prepare a hydrolysis modified solution with the concentration of 2%, and quickly stirring the prepared solution.
Step 3, dissolving
In order to fully dissolve the halogen anions in distilled water/tap water, the prepared hydrolysis modified solution is placed on a magnetic stirrer, heated and stirred for 30min, and then placed in a constant-temperature (293-323K) water bath kettle.
Step 4, hydrolysis hydrogen production
And (3) putting 1g of magnesium-based alloy into the fully dissolved hydrolysis modified solution with the concentration of 2% for hydrolysis hydrogen production test, collecting hydrogen by adopting a drainage method, recording the mass of the hydrogen at intervals of 5s, and finally performing data processing.
Example 2
A green hydrolysis solution of halogen anion hydrolysis medium for preparing hydrogen by hydrolyzing magnesium-based alloy is a 2-5% seawater modification solution, which is distilled water/tap water + M (M is NaF, NaCl, NaBr and NaI), wherein the amount of M is 0.1 mol. The halogen anion hydrolysis modification solution concentration in this embodiment was 5%.
A greenization regulation and control method of a halogen anion hydrolysis medium for magnesium-based alloy hydrolysis hydrogen production comprises the following steps:
step 1, weighing
The amount of the halogen anion substance was 0.1mol, and the mass of the distilled water/tap water and the halogen anion was calculated by the formulas n ═ M/M and c ═ (a/B) × 100% (n is the amount of the substance, M is the molar mass of the substance, M is the mass of the substance, c is the concentration of the solution, a is the mass of the solute, and B is the mass of the solution), and weighed with a balance.
Step 2, preparing a solution
And adding the weighed halogen anions into distilled water/tap water to prepare a hydrolysis modified solution with the concentration of 5%, and quickly stirring the prepared solution.
Step 3, dissolving
In order to fully dissolve the halogen anions in distilled water/tap water, the prepared hydrolysis modified solution is placed on a magnetic stirrer, heated and stirred for 30min, and then placed in a constant-temperature (293-323K) water bath kettle.
Step 4, hydrolysis hydrogen production
And (3) putting 1g of magnesium-based alloy into the fully dissolved hydrolysis modified solution with the concentration of 5% for hydrolysis hydrogen production test, collecting hydrogen by adopting a drainage method, recording the mass of the hydrogen at intervals of 5s, and finally performing data processing.
Example 3
A green hydrolysis solution of halogen anion hydrolysis medium for preparing hydrogen by hydrolyzing magnesium-based alloy is a 2-5% seawater modification solution, which is distilled water/tap water + M (M is NaF, NaCl, NaBr and NaI), wherein the amount of M is 0.1 mol. The halogen anion hydrolysis modification solution concentration in this embodiment was 3.5%.
A greenization regulation and control method of a halogen anion hydrolysis medium for magnesium-based alloy hydrolysis hydrogen production comprises the following steps:
step 1, weighing
The amount of the halogen anion substance was 0.1mol, and the mass of the distilled water/tap water and the halogen anion was calculated by the formulas n ═ M/M and c ═ (a/B) × 100% (n is the amount of the substance, M is the molar mass of the substance, M is the mass of the substance, c is the concentration of the solution, a is the mass of the solute, and B is the mass of the solution), and weighed with a balance.
Step 2, preparing a solution
And adding the weighed halogen anions into distilled water/tap water to prepare a hydrolysis modified solution with the concentration of 3.5%, and quickly stirring the prepared solution.
Step 3, dissolving
In order to fully dissolve the halogen anions in distilled water/tap water, the prepared hydrolysis modified solution is placed on a magnetic stirrer, heated and stirred for 30min, and then placed in a constant-temperature (293-323K) water bath kettle.
Step 4, hydrolysis hydrogen production
And (3) putting 1g of magnesium-based alloy into the fully dissolved hydrolysis modified solution with the concentration of 3.5% for hydrolysis hydrogen production test, collecting hydrogen by adopting a drainage method, recording the mass of the hydrogen at intervals of 5s, and finally performing data processing.
As can be seen from figure 1, the initial hydrolysis rate and the final hydrogen production capacity of the magnesium-based alloy in different halogen anion hydrolysis modification solutions are obviously enhanced, and the advantage of large-scale hydrogen preparation is shown at short time and low temperature.
The method mainly discloses a hydrolysis hydrogen production mechanism of the magnesium-based alloy by researching the influence of different halogen anions on the thermodynamic behavior of the hydrolysis hydrogen production of the magnesium-based alloy and researching the hydrogen production behavior of the magnesium-based alloy at different temperatures, different halogen anions and different valence states, so that a magnesium-based green hydrolysis medium system is optimized, and the initial kinetic performance of the hydrolysis hydrogen production is effectively improved. Destroying Mg (OH) formed on the surface of the magnesium-based alloy by using halogen anions in the hydrolysis solution2The integrity of the membrane is improved on the basis of reducing the cost2The utilization rate of O molecules enables water to continuously contact with fresh magnesium alloy particles for rapid reaction, and the initial kinetics and the final hydrogen production capacity of the hydrolysis hydrogen production of the magnesium-based alloy are promoted.
Different halogen anion hydrolytic solutions are obtained by different halogen anion types, different halogen anion contents, different addition forms and different temperature process parameters, and the magnesium-based alloy can generate different initial hydrogen production dynamics and hydrogen production capacity, namely yield characteristics under different hydrolytic hydrogen production medium conditions. Therefore, the hydrolysis hydrogen production medium can be adjusted by optimizing the halogen anion, so that the hydrolysis characteristic of the magnesium-based alloy can meet the application requirements of various occasions.
Claims (2)
1. A greenization regulation and control method of halogen anion hydrolysis medium for magnesium-based alloy hydrolysis hydrogen production is characterized by comprising the following steps;
step 1, weighing
The amount of the halogen anion substance was 0.1mol, and the mass of the distilled water/tap water and the halogen anion was calculated by the formulas n ═ M/M and c ═ (a/B) × 100% (n is the amount of the substance, M is the molar mass of the substance, M is the mass of the substance, c is the concentration of the solution, a is the mass of the solute, and B is the mass of the solution), and weighed with a balance;
step 2, preparing a solution
Adding the weighed halogen anions into distilled water/tap water to prepare a hydrolysis modified solution with the concentration of 2-5%, and quickly stirring the prepared solution;
step 3, dissolving
In order to fully dissolve the halogen anions in distilled water/tap water, the prepared hydrolysis modified solution is placed on a magnetic stirrer, heated and stirred for 30min and then placed in a constant-temperature (293-323K) water bath kettle;
step 4, hydrolysis hydrogen production
And (3) putting 1g of magnesium-based alloy into the fully dissolved hydrolysis modified solution with the concentration of 2-5% for hydrolysis hydrogen production test, collecting hydrogen by adopting a drainage method, recording the mass of the hydrogen at intervals of 5s, and finally performing data processing.
2. The method for regulating and controlling greenness of the halogen anion hydrolysis medium for hydrogen production by hydrolysis of magnesium-based alloy according to claim 1, wherein the concentration of the hydrolysis modification solution is 2-5%, and the solution is distilled water/tap water + M (M ═ NaF, NaCl, NaBr, NaI), wherein the amount of M is 0.1 mol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594146A (en) * | 2022-08-31 | 2023-01-13 | 榆林学院（Cn） | Efficient seawater acid radical anion regulation and control method for hydrogen production by hydrolysis of waste magnesium-aluminum alloy |
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| CN102491265A (en) * | 2011-12-06 | 2012-06-13 | 南京工业大学 | Method for producing hydrogen by carrying out hydrolysis on magnesium-based material |
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| US20170107101A1 (en) * | 2014-06-13 | 2017-04-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite material for hydrolytically generating hydrogen, device for hydrolytically generating hydrogen, method for generating hydrogen, device for generating electric energy, and possible applications |
| CN106829858A (en) * | 2017-01-16 | 2017-06-13 | 北京科技大学 | A kind of method of the quick hydrogen making of utilization nanoporous magnesium |
| CN110550600A (en) * | 2018-05-31 | 2019-12-10 | 吉林大学 | Aluminum alloy hydrogen production method and application of reaction liquid |
| CN111573621A (en) * | 2020-06-05 | 2020-08-25 | 南京工业大学 | Method for preparing hydrogen by hydrolysis |
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- 2021-02-06 CN CN202110165516.1A patent/CN112850641A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101456535A (en) * | 2007-12-12 | 2009-06-17 | 中国科学院物理研究所 | Method for preparing hydrogen |
| CN102491265A (en) * | 2011-12-06 | 2012-06-13 | 南京工业大学 | Method for producing hydrogen by carrying out hydrolysis on magnesium-based material |
| KR20140072602A (en) * | 2012-12-05 | 2014-06-13 | 한국과학기술원 | Mg alloys and their production method for fast hydrogen generation from hydrolysis in NaCl solution |
| US20170107101A1 (en) * | 2014-06-13 | 2017-04-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Composite material for hydrolytically generating hydrogen, device for hydrolytically generating hydrogen, method for generating hydrogen, device for generating electric energy, and possible applications |
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| CN111573621A (en) * | 2020-06-05 | 2020-08-25 | 南京工业大学 | Method for preparing hydrogen by hydrolysis |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594146A (en) * | 2022-08-31 | 2023-01-13 | 榆林学院（Cn） | Efficient seawater acid radical anion regulation and control method for hydrogen production by hydrolysis of waste magnesium-aluminum alloy |
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