CN112209338A - Preparation method of silicon-based hydrogen production system - Google Patents
Preparation method of silicon-based hydrogen production system Download PDFInfo
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- CN112209338A CN112209338A CN202011114479.3A CN202011114479A CN112209338A CN 112209338 A CN112209338 A CN 112209338A CN 202011114479 A CN202011114479 A CN 202011114479A CN 112209338 A CN112209338 A CN 112209338A
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- silicon
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- hydrogen production
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
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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
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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
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation method of a silicon-based hydrogen production system, which comprises the steps of mechanically ball-milling silicon powder, reducing metal and bismuth salt, carrying out heat treatment, and mixing with ammonium salt to obtain the hydrogen production system; the reducing metal is two or more of lithium, potassium, sodium, calcium, barium and magnesium; and must contain magnesium metal; the bismuth salt being BiCl3,BiF3,BiBr3One or two of BiOCl, BiOF and BiOBr; the ammonium salt being NH4F,NH4Cl,NH4Br,(NH4)2CO3,NH4HCO3One or two of (a); the molar ratio of the reducing metal to silicon is 0.01 to 2, and the molar ratio of the other reducing metals to magnesium is 0.03 to 0.3; the molar ratio of the bismuth salt to the silicon is 0.01-0.15, and the molar ratio of the ammonium salt to the silicon is 0.01-0.2; the hydrogen production material reacts with water, has high hydrogen yield, and can be used for portable hydrogen sources of micro fuel cells.
Description
Technical Field
The invention belongs to the field of hydrogen production, and particularly relates to a preparation method of a silicon-based hydrogen production system.
Background
With the rapid development of the photovoltaic industry, the solar cell panel mainly based on crystalline silicon comes to the end of life. How to effectively treat thousands of tons of silicon panels is a difficult problem to be solved urgently by governments and scientific research personnel all over the world. The silicon reacts with water to produce hydrogen, and the hydrogen is taken as a portable hydrogen source of the fuel cell, which is one of effective methods for solving the problem of scrapped silicon panels. At present, the feasibility evaluation analysis of waste silicon panels and alkaline solution hydrogen production is carried out in the existing literature, 1-3% of portable hydrogen sources can be completely provided for fuel cells, and the processed silicon oxide product can be used as a raw material for preparing a silicon simple substance, so that the cyclic utilization of crystalline silicon-solar panels-silicon dioxide is realized, and the influence of the solar industry on environmental pollution is reduced. However, silicon has low reactivity in the process of reacting with water, and a high-concentration strong alkaline solution or a nano-scale particle size is required to ensure rapid reaction of silicon with water. However, the high-concentration strong alkali solution has potential safety hazard in the use process; and the preparation cost of the nano-silicon particles is higher. Therefore, how to improve the reactivity of silicon and realize the continuous and rapid reaction with water in a neutral solution is the key of the application of the silicon hydrogen production technology.
Magnesium silicon alloys are a common method for preparing porous silicon. Alloying magnesium and silicon, and corroding magnesium metal by using an acid solution to obtain porous silicon with large specific surface area; the silicon material can be used for the cathode of a lithium ion battery. In addition, some literature reports; the corroded porous silicon has high reaction activity in alkali solution due to large specific surface area, and can also be used for portable hydrogen sources. If magnesium-silicon alloy corrosion and silicon and alkali reaction hydrogen production are combined to provide hydrogen, the hydrogen is a hydrogen source with great application prospect. However, the magnesium alloy hydrogen production has the following problems: magnesium metal corrodes to produce hydrogen under acidic condition, while silicon reacts with water in alkaline solution, so that the problem of incompatibility of acid and alkali exists. If magnesium alloy is adopted to react with alkali; while magnesium hydroxide, a hydrolysis product of magnesium, is insoluble in alkali and deposits on the surface of the silicon particles prevent the silicon from continuing to react with water.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon-based hydrogen production system, which overcomes the defects of the prior art and realizes continuous hydrolysis hydrogen production of silicon materials in neutral water or alkalescent solution. In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of the silicon-based hydrogen production system is characterized in thatThe method comprises the following steps: mechanically ball-milling and heat-treating silicon powder, reducing metal and bismuth salt, and mixing with ammonium salt to obtain a hydrogen production system; the reducing metal is two or more of lithium, potassium, sodium, calcium, barium and magnesium; and must contain magnesium metal; the bismuth salt being BiCl3,BiF3,BiBr3One or two of BiOCl, BiOF and BiOBr; (ii) a The ammonium salt being NH4F,NH4Cl,NH4Br,(NH4)2CO3,NH4HCO3One or two of (a); the molar ratio of the reducing metal to silicon is 0.01 to 2, and the molar ratio of the other reducing metals to magnesium is 0.03 to 0.3; the molar ratio of the bismuth salt to the silicon is 0.01-0.15, and the molar ratio of the ammonium salt to the silicon is 0.01-0.2; a method for preparing a silicon-based hydrogen production system, comprising:
1) weighing silicon powder, reducing metal and bismuth salt with certain mol, and mechanically ball-milling for 1-10h in argon atmosphere;
2) tabletting the product obtained in the step 1), heating to 800 ℃ in an argon atmosphere, and keeping the temperature for 5-20 h;
3) crushing the product obtained in the step 2), and mechanically ball-milling the crushed product with ammonium salt with a certain mole for 1 to 10 hours; obtaining the silicon-based hydrogen production system.
The method adopts reduction metal, bismuth salt and ammonium salt as a synergistic system to promote magnesium and silicon to continuously react in an aqueous solution to generate hydrogen; the reducing metal has high reaction activity in water and can be used as a reaction active point for magnesium-silicon alloy hydrolysis; the bismuth salt can provide a metal bismuth cathode, and forms a micro corrosion battery with magnesium silicon in the hydrolysis process, so that the electrochemical corrosion of the magnesium silicon is promoted to produce hydrogen; the ammonium salt provides high-concentration electrolyte to participate in the reaction of magnesium silicon and water; in addition, ammonia and magnesium are easy to form a complex, and the deposition of magnesium hydrolysate on the surface of magnesium silicon is effectively prevented. Compared with other hydrogen production materials, the invention has the following advantages:
1) the silicon-based hydrogen production material disclosed by the invention reacts with water to generate hydrogen, is simple in process and convenient to operate, and is beneficial to industrial production.
2) The silicon hydrogen production material does not directly use strong alkaline solution, does not generate potential safety hazard to users, and has low requirement on the material of hydrogen production equipment.
3) The silicon-based hydrogen production material uses the magnesium-silicon alloy, the preparation process is mature, and the cost of the silicon-based hydrogen production material is greatly reduced.
4) The silicon hydrogen production material has good hydrolysis performance in neutral aqueous solution, and can completely provide portable hydrogen source for fuel cells.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following embodiments are described in detail as follows:
example 1
The component design of a silicon-based hydrogen production system is as follows:
1) 0.02mol of silicon powder; 0.01mol of magnesium powder; 0.002mol of lithium; 0.001mol of bismuth trichloride; 0.001mol of ammonium chloride;
2) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of lithium; 0.001mol of bismuth trichloride; 0.002mol of ammonium chloride;
3) 0.02mol of silicon powder; 0.03mol of magnesium powder; 0.003mol of lithium; 0.001mol of bismuth trichloride; 0.003mol of ammonium chloride;
a method for preparing a silicon-based hydrogen production system, comprising:
1) weighing silicon powder, magnesium powder, lithium sheets and bismuth salt in certain molar ratio, and mechanically ball-milling for 10 hours in argon atmosphere;
2) tabletting the product obtained in the step 1), heating to 600 ℃ in an argon atmosphere, and keeping the temperature for 5 hours;
3) crushing the product obtained in the step 2), and mechanically ball-milling the crushed product with ammonium chloride with a certain mole for 5 hours; obtaining the silicon-based hydrogen production system.
Weighing 0.3g of sample, and putting the sample into neutral water, thereby having good hydrolysis hydrogen production performance.
Example 2
The component design of a silicon-based hydrogen production system is as follows:
4) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of sodium; 0.001mol of bismuth trichloride; 0.0015mol of ammonium chloride;
5) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of potassium; 0.001mol of bismuth trichloride; 0.0015mol of ammonium chloride;
6) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of calcium; 0.001mol of bismuth trichloride; 0.0015mol of ammonium chloride;
a method for preparing a silicon-based hydrogen production system, comprising:
1) weighing silicon powder, magnesium powder, lithium sheets and bismuth salt in certain molar ratio, and mechanically ball-milling for 10 hours in argon atmosphere;
2) tabletting the product obtained in the step 1), heating to 700 ℃ in an argon atmosphere, and keeping the temperature for 1 h;
3) crushing the product obtained in the step 2), and mechanically ball-milling the crushed product with ammonium chloride with a certain mole for 10 hours; obtaining the silicon-based hydrogen production system. Weighing 0.3g of sample, and putting the sample into neutral water, thereby having good hydrolysis hydrogen production performance.
Example 3
The preparation method is the same as that of example 1
The component design of a silicon-based hydrogen production system is as follows:
7) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of lithium; 0.001mol of bismuth oxychloride; 0.0015mol of ammonium fluoride;
8) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of barium; 0.001mol of bismuth tribromide; 0.0015mol of ammonium carbonate;
9) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of calcium; 0.001mol of bismuth oxybromide; 0.0015mol of ammonium bromide;
10) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of calcium; 0.001mol of bismuth oxyfluoride; 0.0015mol of ammonium bicarbonate;
11) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of lithium; 0.001mol of calcium; 0.001mol of bismuth oxychloride; 0.0015mol of ammonium fluoride;
12) 0.02mol of silicon powder; 0.02mol of magnesium powder; 0.001mol of lithium; 0.0005mol of sodium; 0.001mol of bismuth tribromide; 0.0015mol of ammonium carbonate;
weighing 0.3g of sample, and putting the sample into neutral water, thereby having good hydrolysis hydrogen production performance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1. A preparation method of an aluminum-silicon-based hydrogen production system is characterized by comprising the following steps: taking aluminum powder, soluble inert metal salt and silicon powder as raw materials, mechanically mixing, sintering at high temperature in argon atmosphere, and mechanically ball-milling with alkali and metal villiaumite to obtain an aluminum-silicon-based hydrogen production system; the molar ratio of the aluminum powder to the silicon is 0.3-3; the soluble inert metal halide salt is one or two of bismuth chloride, stannic fluoride, stannous fluoride, stannic chloride, stannous chloride, copper fluoride, silver fluoride, indium fluoride and gallium fluoride; the molar ratio of the soluble inert metal halide salt to the aluminum is 0.01-0.1; the alkali is one or two of sodium hydroxide, potassium hydroxide, calcium hydroxide and lithium hydroxide; the metal fluoride salt is one of sodium fluoride, potassium fluoride, lithium fluoride and ammonium fluoride; the molar ratio of the alkali to the aluminum silicon is 0.01-0.2; the molar ratio of the metal fluoride salt to the aluminum silicon is 0.01-0.1; a preparation method of an aluminum-silicon-based hydrogen production system comprises the following steps:
1) weighing aluminum powder, silicon powder and soluble inert metal halide salt with certain mol, and mechanically ball-milling for 1-10h in argon atmosphere;
2) tabletting the product obtained in the step 1), heating the product to 800 ℃ in an argon atmosphere, and keeping the temperature for 5-20 h;
3) crushing the product obtained in the step 2), and mechanically ball-milling the crushed product with alkali and metal villiaumite for 1 to 20 hours; an aluminum silicon-based hydrogen production system.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124000A (en) * | 2022-08-25 | 2022-09-30 | 世能氢电科技有限公司 | Preparation method of magnesium-based hydrogen storage material and magnesium-based hydride prepared by same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669695A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of copper bismuth silicon catalyst |
| CN107188123A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon/alkali metal hydrogen manufacturing material |
| CN107188124A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon substrate hydrogen manufacturing material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669695A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of copper bismuth silicon catalyst |
| CN107188123A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon/alkali metal hydrogen manufacturing material |
| CN107188124A (en) * | 2017-01-06 | 2017-09-22 | 中国计量大学 | A kind of preparation method of silicon substrate hydrogen manufacturing material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124000A (en) * | 2022-08-25 | 2022-09-30 | 世能氢电科技有限公司 | Preparation method of magnesium-based hydrogen storage material and magnesium-based hydride prepared by same |
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