CN109650331A - Hydrogen production process and hydrogen generating system based on silicon powder and silicon material - Google Patents
Hydrogen production process and hydrogen generating system based on silicon powder and silicon material Download PDFInfo
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- CN109650331A CN109650331A CN201910119236.XA CN201910119236A CN109650331A CN 109650331 A CN109650331 A CN 109650331A CN 201910119236 A CN201910119236 A CN 201910119236A CN 109650331 A CN109650331 A CN 109650331A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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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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Abstract
The invention discloses a kind of hydrogen production process and hydrogen generating system based on silicon powder and silicon material, the described method includes: S1, silicon powder is put into aqueous slkali, reacted under the conditions of the first temperature T1, generate sodium metasilicate and hydrogen, and heat is discharged during the reaction, aqueous slkali temperature increases；S2, after aqueous slkali temperature is increased to preset temperature threshold T0, silicon material is put into aqueous slkali, is reacted under the conditions of second temperature T2, sodium metasilicate and hydrogen are generated.Hydrogen production process in the present invention entirely produces and reaction process has the advantages that no pollution, zero-emission, not power consumption；Hydrogen production process is simple, can sufficiently recycle waste silicon powder, useless silicon material and the making herbs into wool waste liquid of photovoltaic industry, have many advantages, such as at low cost, reduction pollution, easily storage and transport, have very extensive purposes in mobile hydrogen generator station and industrial hydrogen production field.
Description
Technical field
The invention belongs to hydrogen producing technology field, especially a kind of hydrogen production process and hydrogen generating system based on silicon powder and silicon material.
Background technique
Hydrogen Energy is a kind of clean energy resource of great application potential, and countries in the world all put into substantial contribution and researched and developed.Hydrogen manufacturing
Technology is the most important sport technique segment of hydrogen utilization.Currently, hydrogen producing technology includes the methods of chemistry, biology, electrolysis, photodissociation.Example
Such as:
1, water electrolysis hydrogen production
Water electrolysis hydrogen producing is relatively wide and comparative maturity one of the method for current application.Water is that raw material hydrogen production process is hydrogen and oxygen
Burning generate water inverse process, as long as therefore provide the certain energy of certain forms, water decomposition can be made.There is provided electric energy makes water decomposition
The efficiency of hydrogen is made generally in 75-85%, technical process is simple, pollution-free, but it is big to consume electricity, therefore its application by
Certain limitation.
2, fossil fuel hydrogen manufacturing
It is the main method of current hydrogen making using coal, petroleum and natural gas as waste hydrogen, this method is in China
All there is mature technique, and have industrial production equipment.
2.1 using coal as waste hydrogen
In China's energy resource structure, within significant period of time from now on, coal will also be main energy sources.Hydrogen production from coal gasification
Refer to that coal under high-temperature pressure or pressurization, reacts with gasifying agent and is converted to gaseous product.Gasifying agent be water vapour or oxygen (air),
It is different with different gasification process containing components, contents such as hydrogen in gaseous product.But the method investment is big, pollutant discharge amount
Greatly, water consumption is big, is suitble to extensive hydrogen gas production.
2.2 using natural gas or light oil as waste hydrogen
This method is to convert that hydrogen is made in the presence of a catalyst with steam reaction, and reaction carries out at 800-820 DEG C.
There is hydrogen partial from water vapour.In the gas composition made from this method, hydrogen volume content is up to 74%, production cost
Cost of material is depended primarily on, China's light oil price is high, and gas cost processed is expensive, has certain limitations using this method.It is most of big
It is raw material that type ammonia synthesis methanol plant, which is all made of natural gas, and the technique of catalytic water producing hydrogen from steam conversion is original with petroleum and natural gas
Expect that the technique of hydrogen manufacturing is very mature, but produces industrial chemicals because being limited to be currently used primarily in by raw material.
Currently, the solar-grade silicon ingot yield in China is more than 500,000 tons, generated about during silicon ingot is cut into silicon wafer
The silicon powder of half, due to mixing other chemical substances, recycles although the silicon powder purity of these micron dimensions is up to 99.9999%
It is at high cost, it is often used as waste disposal, processing cost Gao Binghui brings certain environment to influence.In addition, photovoltaic industry is gone back every year
Generate largely useless silicon wafer, useless silicon rod, useless silicon ingot etc..Therefore, it is badly in need of finding a kind of waste silicon powder and useless silicon material of can be improved
The technology of added value.
Therefore, in view of the above technical problems, it is necessary to which a kind of hydrogen production process based on silicon powder and silicon material and hydrogen manufacturing system are provided
System.
Summary of the invention
In view of the shortcomings of the prior art, the purpose of the present invention is to provide a kind of hydrogen production process and system based on silicon powder and silicon material
Hydrogen system.
To achieve the goals above, the technical solution that one embodiment of the invention provides is as follows:
A kind of hydrogen production process based on silicon powder and silicon material, which comprises
S1, silicon powder is put into aqueous slkali, is reacted under the conditions of the first temperature T1, generate sodium metasilicate and hydrogen,
And heat is discharged during the reaction, aqueous slkali temperature increases；
S2, after aqueous slkali temperature is increased to preset temperature threshold T0, silicon material is put into aqueous slkali, in second temperature T2
Under the conditions of reacted, generate sodium metasilicate and hydrogen.
As a further improvement of the present invention, the first temperature T1 meets 8 DEG C≤T1≤25 DEG C.
As a further improvement of the present invention, the preset temperature threshold TO is 40 DEG C, and second temperature T2 meets T2 >=40
℃。
As a further improvement of the present invention, the silicon powder is the silicon powder that partial size is less than or equal to 1 μm.
As a further improvement of the present invention, the silicon material is silicon wafer, silicon rod or silicon ingot.
As a further improvement of the present invention, the aqueous slkali be mass concentration more than or equal to 0.5% KOH solution or
NaOH solution.
As a further improvement of the present invention, the step S1 further include:
Solid base is added in the reaction system of silicon powder and aqueous slkali, to improve solution temperature.
As a further improvement of the present invention, the method also includes:
Hydrogen obtained in collection step S1 and/or step S2.
As a further improvement of the present invention, the method also includes:
Solution after cooling reaction, sodium metasilicate and water, which combine, obtains waterglass.
Another embodiment of the present invention provides technical solution it is as follows:
A kind of hydrogen generating system based on silicon powder and silicon material, the system comprises: reactive tank, positioned at the alkali soluble of reaction front of the slot
Liquid pipe road, the silicon powder dispensing port on reactive tank and silicon material dispensing port, hydrogen recovery channel and water positioned at reactive tank rear end
Glass recovery channel and the hydrogen gas recovering device being connected with hydrogen recovery channel, aqueous slkali are entered anti-by aqueous slkali channel
It answers in slot, silicon powder and silicon material pass through silicon powder dispensing port respectively and silicon material dispensing port enters in reactive tank and reacted with aqueous slkali,
The hydrogen that reaction generates is entered in hydrogen gas recovering device by hydrogen recovery channel, and waterglass is carried out by waterglass recovery channel
It collects.
The beneficial effects of the present invention are:
Hydrogen production process in the present invention entirely produces and reaction process has the advantages that no pollution, zero-emission, not power consumption；
Hydrogen production process is simple, can sufficiently recycle waste silicon powder, useless silicon material and the making herbs into wool waste liquid of photovoltaic industry, have at
The advantages that this low, reduction pollution, easily storage and transport, there is very extensive use in mobile hydrogen generator station and industrial hydrogen production field
On the way；
It can further be recycled while obtaining high-purity hydrogen and obtain byproduct water glass.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the specific flow chart of hydrogen production process in the present invention；
Fig. 2 is the structural schematic diagram of hydrogen generating system in the present invention.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, below in conjunction with of the invention real
The attached drawing in example is applied, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work, all should belong to protection of the present invention
Range.
Join shown in Fig. 1, the invention discloses a kind of hydrogen production process based on silicon powder and silicon material, comprising:
S1, silicon powder is put into aqueous slkali, is reacted under the conditions of the first temperature T1, generate sodium metasilicate and hydrogen,
And heat is discharged during the reaction, aqueous slkali temperature increases, reaction equation are as follows:
Si+2NaOH+H2O=Na2SiO3+2H2↑；
S2, after aqueous slkali temperature is increased to preset temperature threshold T0, silicon material is put into aqueous slkali, in second temperature T2
Under the conditions of reacted, generate sodium metasilicate and hydrogen, reaction equation are as follows:
Si+2NaOH+H2O=Na2SiO3+2H2↑。
Preferably, the first temperature T1 in the present invention meets 8 DEG C≤T1≤25 DEG C；Preset temperature threshold TO is 40 DEG C, the
Two temperature T2 meet T2 >=40 DEG C.
Wherein, silicon powder is that partial size less than or equal to 1 μm controls gold silicon rank silicon powder, and aqueous slkali is that mass concentration is greater than or waits
In 0.5% KOH solution or NaOH solution.The recycling of the making herbs into wool waste liquid in photovoltaic manufacturing process can be used in aqueous slkali, can
Turned waste into wealth with recycling；Also the certain density aqueous slkali newly matched can be used.Process for etching in photovoltaic manufacturing process
Every line generates 2 tons or more aqueous slkalis daily, and the cell piece factory of a 4GW just has about 8 tons of making herbs into wool waste liquid that can add for one day
To utilize.
Silicon material is silicon wafer, silicon rod or silicon ingot, and silicon wafer, silicon rod or silicon ingot can be the leftover pieces in photovoltaic industry chain or control
Gold silicon does not have particular/special requirement to purity of silicon.
Step S1 is carried out in cryogenic conditions, and reaction temperature is generally below room temperature, if can be in silicon under the conditions of extreme low temperature
Solid base is added in the reaction system of powder and aqueous slkali, to improve the requirement that solution temperature reaches triggering reaction.
It can react to obtain hydrogen in step S1 and S2 of the invention, hydrogen can be realized by hydrogen gas recovering device
It collects.In addition, the solution after cooling reaction, sodium metasilicate and water combine and obtain waterglass, reaction equation are as follows:
Na2SiO3+9H2O=Na2SiO3·9H2O。
Join shown in Fig. 2, the invention also discloses a kind of hydrogen generating system based on silicon powder and silicon material, comprising: reactive tank 10, position
In aqueous slkali pipeline 20, the silicon powder dispensing port 31 on reactive tank and the silicon material dispensing port 32 of reaction front of the slot, positioned at reaction
The hydrogen recovery channel 41 and waterglass recovery channel 42 of slot rear end and the hydrogen being connected with hydrogen recovery channel 41 recycling dress
Set 43.
According to above-mentioned hydrogen production process, aqueous slkali is entered in reactive tank by aqueous slkali channel, and silicon powder and silicon material pass through respectively
Silicon powder dispensing port and silicon material dispensing port enter in reactive tank to be reacted with aqueous slkali, and the hydrogen for reacting generation is recycled by hydrogen
Pipeline enters in hydrogen gas recovering device, and waterglass is collected by waterglass recovery channel.
Hydrogen production process in the present invention passes through silicon powder first and aqueous slkali reacts, and the silicon powder of small particle has specific surface
The big feature of product is easy to trigger reacting for silicon and alkali.Silicon powder and aqueous slkali can react generation sodium metasilicate under cryogenic
With hydrogen and discharge heat, the heat discharged aqueous slkali can be accelerated with silicon powder the reaction was continued.After reaction carries out a period of time
Solution temperature be raised to after preset temperature threshold or more can using silicon materials such as silicon wafer, silicon rod or silicon ingots the reaction was continued carrys out hydrogen manufacturing.
The heat for reacting release with aqueous slkali using silicon powder in entire reaction process carries out the heating of reaction system, is not necessarily to
It is heated by external device (ED), greatly reduces the cost of hydrogen manufacturing.
As in a specific embodiment of the invention, hydrogen production process includes:
S1, silicon powder is put into aqueous slkali, is reacted under cryogenic, generate sodium metasilicate and hydrogen, and anti-
Heat should be discharged in the process, and aqueous slkali temperature increases.
Specifically, silicon powder is the silicon powder generated during silicon ingot is cut into silicon wafer in the present embodiment, and silicon powder is that partial size is small
Gold silicon rank silicon powder is controlled in or equal to 1 μm；Aqueous slkali is the making herbs into wool waste liquid in photovoltaic manufacturing process, and aqueous slkali is mass concentration
About 1.5% KOH solution or NaOH solution.
Cryogenic conditions in this step are the condition lower than room temperature, if the initial aqueous slkali temperature in the present embodiment is 8 DEG C,
With heat is discharged in silicon powder and aqueous slkali reaction process, the temperature of solution can be gradually risen.
S2, after aqueous slkali temperature is increased to preset temperature threshold, silicon material is put into aqueous slkali, under the high temperature conditions into
Row reaction, generates sodium metasilicate and hydrogen.
Silicon material in the present embodiment is silicon wafer, silicon rod or silicon ingot, and silicon wafer, silicon rod or silicon ingot are the corners in photovoltaic industry chain
Expect or control gold silicon.
Silicon material will usually carry out under the high temperature conditions with reacting for aqueous slkali, and reaction temperature is generally higher than 40 DEG C.With
The heat discharged in silicon powder and aqueous slkali reaction process, solution temperature can gradually rise to 40 DEG C of preset temperature threshold, and temperature reaches
To after 40 DEG C or more, can be reacted by silicon rod or silicon ingot with the blocky silicon material such as aqueous slkali.
Silicon powder and silicon material in the present embodiment are the waste material in photovoltaic industry chain, and aqueous slkali is making herbs into wool waste liquid, entire to produce
Have the advantages that no pollution, zero-emission, not power consumption with reaction process.
It is calculated by experiment, every 100,000 tons of waste silicon powders and useless silicon material can 1.4 ten thousand tons of High Purity Hydrogens processed, sodium metasilicate (Na2SiO3)
440000 tons, about 1,600,000,000 yuan of the gross output value；Wherein, only about 600,000,000 yuan of cost.
It should be understood that the high temperature in low temperature and step S2 in the present embodiment in step S1 is respectively with 8 DEG C and 40 DEG C
For be illustrated, in other embodiments, low temperature and high temperature can be for lower than room temperatures and higher than other temperature of room temperature, herein
No longer citing is illustrated one by one.
In addition, the temperature of reaction system can be promoted by adding solid base under extreme low temperature condition (as being lower than 8 DEG C)
Degree reaches the requirement that triggering silicon is reacted with aqueous slkali.
As can be seen from the above technical solutions, the invention has the following advantages:
Hydrogen production process in the present invention entirely produces and reaction process has the advantages that no pollution, zero-emission, not power consumption；
Hydrogen production process is simple, can sufficiently recycle waste silicon powder, useless silicon material and the making herbs into wool waste liquid of photovoltaic industry, have at
The advantages that this low, reduction pollution, easily storage and transport, there is very extensive use in mobile hydrogen generator station and industrial hydrogen production field
On the way；
It can further be recycled while obtaining high-purity hydrogen and obtain byproduct water glass.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. a kind of hydrogen production process based on silicon powder and silicon material, which is characterized in that the described method includes:
S1, silicon powder is put into aqueous slkali, is reacted under the conditions of the first temperature T1, generation sodium metasilicate and hydrogen, and
Heat is discharged in reaction process, aqueous slkali temperature increases；
S2, after aqueous slkali temperature is increased to preset temperature threshold T0, silicon material is put into aqueous slkali, in second temperature T2 condition
Under reacted, generate sodium metasilicate and hydrogen.
2. the hydrogen production process according to claim 1 based on silicon powder and silicon material, which is characterized in that the first temperature T1 is full
8 DEG C≤T1≤25 DEG C of foot.
3. the hydrogen production process according to claim 1 based on silicon powder and silicon material, which is characterized in that the preset temperature threshold
TO is 40 DEG C, and second temperature T2 meets T2 >=40 DEG C.
4. the hydrogen production process according to claim 2 based on silicon powder and silicon material, which is characterized in that the silicon powder is that partial size is small
In or equal to 1 μm of silicon powder.
5. the hydrogen production process according to claim 3 based on silicon powder and silicon material, which is characterized in that the silicon material be silicon wafer,
Silicon rod or silicon ingot.
6. the hydrogen production process according to claim 1 based on silicon powder and silicon material, which is characterized in that the aqueous slkali is quality
Concentration is greater than or equal to 0.5% KOH solution or NaOH solution.
7. the hydrogen production process according to claim 2 based on silicon powder and silicon material, which is characterized in that the step S1 is also wrapped
It includes:
Solid base is added in the reaction system of silicon powder and aqueous slkali, to improve solution temperature.
8. the hydrogen production process according to claim 1 based on silicon powder and silicon material, which is characterized in that the method also includes:
Hydrogen obtained in collection step S1 and/or step S2.
9. the hydrogen production process according to claim 1 based on silicon powder and silicon material, which is characterized in that the method also includes:
Solution after cooling reaction, sodium metasilicate and water, which combine, obtains waterglass.
10. a kind of hydrogen generating system based on silicon powder and silicon material, which is characterized in that the system comprises: reactive tank is located at reactive tank
The aqueous slkali pipeline of front end, the silicon powder dispensing port on reactive tank and silicon material dispensing port, the hydrogen positioned at reactive tank rear end return
Closed tube road and waterglass recovery channel and the hydrogen gas recovering device being connected with hydrogen recovery channel, aqueous slkali pass through aqueous slkali
Channel enters in reactive tank, silicon powder and silicon material pass through silicon powder dispensing port respectively and silicon material dispensing port enter in reactive tank with aqueous slkali
It is reacted, the hydrogen for reacting generation is entered in hydrogen gas recovering device by hydrogen recovery channel, and waterglass is returned by waterglass
Closed tube road is collected.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110627016A (en) * | 2019-11-05 | 2019-12-31 | 无锡机电高等职业技术学校 | Method for producing hydrogen by using solid powder hydrogen production agent |
| WO2022242643A1 (en) * | 2021-05-19 | 2022-11-24 | Epro Development Limited | A process and apparatus for the production of hydrogen |
| CN116140061A (en) * | 2023-03-10 | 2023-05-23 | 西安旭旌再生资源有限公司 | Hydrogen production waste liquid separation and recycling device |
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