CN101456535B - Method for preparing hydrogen - Google Patents

Method for preparing hydrogen Download PDF

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CN101456535B
CN101456535B CN2007101792934A CN200710179293A CN101456535B CN 101456535 B CN101456535 B CN 101456535B CN 2007101792934 A CN2007101792934 A CN 2007101792934A CN 200710179293 A CN200710179293 A CN 200710179293A CN 101456535 B CN101456535 B CN 101456535B
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hydrogen
preparation
alloy
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manufacturing container
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CN101456535A (en
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孟庆波
李泓
陈立泉
李冬梅
罗艳红
王兆翔
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Institute of Physics of CAS
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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 relates to a method for preparing hydrogen. The high-purity hydrogen can be produced by soaking a metal or an alloy thereof or a mixture thereof in water, methanol, ethanol or any mixture thereof added with little amount of iodine, bromine or interhalogen compounds. The method has the advantages of simple preparation method, low cost, high yield, high hydrogen production speed, high purity, low energy consumption, environmental protection, easy reclamation of the product and easy regeneration of additive, suitability for large-scale industrialized production and the like. The produced hydrogen can be used in a hydrogen engine and a hydrogen-oxygen fuel cell.

Description

A kind of preparation method of hydrogen
Technical field
The present invention relates to the technology of preparing of hydrogen, particularly utilize chemical reaction to prepare the preparation method of high-purity hydrogen.
Background technology
The energy is the source of human social activity.Based on the modern energy resource system of oil and coal, because distribution of resource is too concentrated and be exhausted day by day, deep energy dilemma is taking place.At present, countries in the world are all exploring the new energy energetically, as sun power, tidal energy, Geothermal energy, nuclear energy etc.For making these new forms of energy obtain effectively, easily utilizing, also the secondary energy that adapt with it to be arranged.Hydrogen energy source is exactly a kind of ideal secondary energy, and it has many advantages: the 1. thermal value height of hydrogen burning, every kg of hydrogen gas firing can produce the heat of about 143KJ, approximately is 3 times of equal in quality gasoline combustion heat.The temperature of combustion zone is wide, is adapted to multiple use.2. products of combustion is a water, and is nontoxic, free from environmental pollution, and is natural circulation, do not destroy resource, is a kind of fuel of cleaning.3. the raw material of producing hydrogen is a water, and aboundresources generates water again after the burning, and natural circulation is fast.4. can do the medium that stores of sun power, electric energy, nuclear energy.5. of many uses, liquid hydrogen can be used as the fuel of firing a rocket, and directly makes automobile, the aircraft of fuel with hydrogen and is also trying out.The hydrogen-oxygen fuel cell that with hydrogen is fuel plays a key effect for the development that promotes electromobile just in whole world broad research.
The production of hydrogen has formed suitable scale.About 5000 billion cubic meters of world's hydrogen output, natural gas hydrogen preparation 2400 billion cubic meters wherein, account for 48%, petroleum reforming hydrogen manufacturing 1500 billion cubic meters, account for 30%, gasification hydrogen manufacturing 900 billion cubic meters account for 18%, and adopt renewable energy source hydrogen manufacturing (as biomass gasification technology and electrolytic process hydrogen manufacturing) only to account for 5% (200 billion cubic meter).But at present hydrogen uses as industrial chemicals mostly, and uses as Hydrogen Energy, only limits to space flight oxyhydrogen engine and present a spot of hydrogen energy automobile and small hydropower station as demonstration.Because fossil oil (oil, Sweet natural gas and coal) reformation hydrogen production, with low costly (be approximately 1.5 yuan/m as water-gas hydrogen manufacturing cost 3H 2), therefore hydrogen makes from fossil oil mostly at present.Because the fossil oil carbon containing will produce carbonic acid gas in the hydrogen production process inevitably, and with the source of water as hydrogen, environmental sound, so water decomposition hydrogen manufacturing is than the more environmental protection of fossil oil reformation hydrogen production, cleaning more, but its power consumption is big, the cost height, as the water electrolysis hydrogen production energy consumption up to 4.5kWh/m 3H 2Therefore hydrogen producing technology need be resolved the contradiction between low cost and high energy efficiency, low-carbon (LC) or zero carbon emission.
International previous work mainly is around fuel cell car on-board hydrogen source unfolded, external big motor corporation and oil company such as GM, Toyota, Daimler Chrysler, Johnson Matthey, Mitsubishi etc., all having carried out this type of research and having developed with methyl alcohol, gasoline etc. is the vehicle-mounted reformation hydrogen production apparatus for demonstrating of raw material.Yet these technology are because its technical difficulty is too big, cost is too high and the Infrastructure input is huge, and practical application can't come into the market in the short period of time.
Calculate according to " from the oil well to the wheel " life cycle methodology, if will make the whole service efficiency of fuel cell car be higher than fuel vehicle, reach more than 40%, its hydrogen production efficiency must at first reach 70%, therefore to improve the competitive power of Hydrogen Energy, must improve hydrogen production efficiency greatly, reduce cost and the optimization system integrated technology.
Hydrogen storage technology is one of main bottleneck of Hydrogen Energy application.Chu Qing can be divided into fixed storage hydrogen and portable storage hydrogen by application class, and the latter is harsher than the former technical requirements, and vehicle-mounted hydrogen storage technology is to realize one of topmost technological challenge that Hydrogen Energy practicability is faced.
The high pressure gas hydrogen storage technology is at present proven technique.The external composite material light hydrogen container storage hydrogen that adopts, the storage hydrogen pressure can reach 35 MPas, and it is in service successfully to be applied to the fuel battery passenger car demonstration in the U.S., Japan and European Union.Recently, 70 MPa hydrogen containers also are in the middle of the examination of laboratory.China has developed 40 MPa hydrogen container samples, but this technology volume storage hydrogen rate is lower, even under 70 MPas, its volume storage hydrogen rate also only is 38kg/m 3H 2Adopt low temperature storage tank to store liquid hydrogen, its volume hydrogen-storage density is than high-pressure hydrogen storing height.Bayerische Motorne Werke Aktiengeellschaft is used for Porvetto 2003 fuel-cell vehicles as hydrogen source.The main drawback of this method is: expended about 30% energy in the liquefaction of hydrogen process, liquid hydrogen evaporation simultaneously causes the loss of hydrogen also to bring potential safety hazard, greatly reduces the practicality of liquid hydrogen storage hydrogen.What really can finally satisfy the requirement of vehicle-mounted storage hydrogen may be solid-state storage hydrogen, is about to storing hydrogen in metal hydride, chemical hydrogen storage material and nano structural material.Can solid-state storage hydrogen has quite high volume hydrogen-storage density, but obtain practical application, depends on whether it satisfies high weight storage hydrogen rate, and can put hydrogen and fill condition such as hydrogen in facility under the mild conditions.Though existing more than 2000 kind of element, intermetallic compound and alloy can form hydride, yet, the material that can satisfy the requirement of vehicle-mounted storage hydrogen also do not found at present.In solid-state storage hydrogen, new ideas have been produced, i.e. the hydrogen capsule in the recent period.This provides possibility for solid-state storage hydrogen near the hydrogen-storage amount of methane.Some novel materials such as alanate, hydroborate and imide scheduling theory hydrogen-storage amount are all quite high, may make solid-state hydrogen storage technology produce new breakthrough.The U.S., European Union and Japan just are being devoted to the research of these novel hydrogen storage materials, NaAlH at present 4Be lower than the hydrogen that just can emit 3.4wt% under 100 ℃ of conditions.U.S. Millennium Cell Inc. (Millennium Cell) proposes with the sodium borohydride catalyzing hydrolyzation hydrogen manufacturing hydrogen source of battery that acts as a fuel, and has set up apparatus for demonstrating.It is the fuel cell fire-fighting concept car of hydrogen source that sign motor corporation (Peugeot) has put on display with the sodium borohydride solution catalytic hydrolysis.
The storage of hydrogen is the main bottleneck that Hydrogen Energy is used, and relevant at present scientific and technical personnel just strengthen research and development capabilities, and breaks through in the hope of obtaining hydrogen storage technology.In March, 2006, USDOE is announced invest 6,000,000 dollars and is carried out vehicle-mounted hydrogen storage technology research, and emphasis is that existing alloy, chemistry are stored up that existing modes such as hydrogen and carbon material Chu Qing are improved and perfect.
The transportation cost of hydrogen is high in addition.The conveying of hydrogen can be divided into the gaseous hydrogen conveying, liquid hydrogen is carried and solid-state hydrogen is carried.Wherein gaseous hydrogen conveying and liquid hydrogen conveying are two kinds of defeated hydrogen modes using at present.Gaseous hydrogen and liquid hydrogen can pass through pipe-line transportation, or carry by large-scale transportation means.The U.S. has about 700 miles Hydrogen Line network, and Europe also has 1000 miles hydrogen feeding pipe road.Technically, Hydrogen Line network installation and maintenance and natural gas line have very big similarity, but exist on price than big-difference, and the Argonne national laboratories research shows that the cost of Hydrogen Line is approximately 30～1,400,000 dollars/mile.And the cost of natural gas line network is ten thousand dollars/mile of 20-80.The ground transport liquid hydrogen mainly is subject to the carrying capacity that is used for the transportation of hydrogen gas vehicle at present.Maximum liquid hydrogen carrier vehicle once only can transport 3.6 tons of hydrogen, and gasoline carrying vehicle once can transport 30 tons of fuel.Therefore, to transport the cost of hydrogen very high on ground.Energy supplier and service station company have started to develop the hydrogen hydrogen aerator at present.European Union is the annual funds that drop into 5000～6,000 ten thousand Euros of these project implementations, and United States Government plans and the annual in the works fund that drops into 1.6 hundred million dollars of SECA at FreedomCar, and Japan will drop into 2,400,000,000 dollars of exploitations that are used for similar techniques in 28 years.
As can be seen from the above, although the Hydrogen Energy utilization has fine prospect, this type of technology is competitively developed in countries in the world, at present with hydrogen do that fuel subject matter is that the hydrogen manufacturing cost is too high, the storage of hydrogen, transportation, release.
Summary of the invention
The objective of the invention is to improve prior art and provide a kind of with low cost, the productive rate height, the purity height, energy consumption is low, environmental friendliness, product is easy to reclaim, additive is easy to regeneration, is fit to the hydrogen preparation method of large-scale industrial production.The hydrogen that produces can use in hydrogen engine, hydrogen-oxygen fuel cell.
Purpose of the present invention can realize by the following method that this method may further comprise the steps:
(1) selects M 1 xM 2 yM 3 zM 4 wO vA kind of or its mixture of metal or alloy produces the hydrogen material as activity; The expression of mixture is designated as M 1 x/ M 2 y/ M 3 z/ M 4 w/ O v"/" represents " mixing " in the present invention.
In the formula:
M 1Be selected from Mg, Al, Zn, Fe, the Sn element,
M 2, M 3, M 4Be selected from Mg, Al, Zn, Fe, Sn, Ga, In, Bi, Pb, the Ti element,
O is an oxygen element, is the oxygen in the zone of oxidation on metal or alloy surface.
X, y, z, w, v are the atomic molar umber, 0.5≤x≤1,0≤(y, z, w)≤0.5 and x+y+z+w=1; 0≤v≤0.1, M 1≠ M 2≠ M 3≠ M 4The metal or alloy powder can be powder, silk, line, rod, piece, porous material, and the shape of material, microtexture can not influence the productive rate of reaction, but the kinetics that big specific surface area can help reacting.
(2) select water (H 2O), methyl alcohol (CH 3OH), ethanol (CH 3CH 2OH) a kind of or or its mixture as hydrogen source material; Mix and do not need special process or step, directly two or three solvent physical mixed is evenly got final product.Can know that according to chemical knowledge these three kinds of solvents can dissolve each other with arbitrary proportion.
(3) select iodine (I 2), bromine (Br 2), a kind of or its mixture of iodine bromine (IBr) is as active additive;
Activity is produced in the hydrogen manufacturing container that the hydrogen material is positioned over an airtight band liquid adding hole and vent valve, with a kind of hydrogen source material and a kind of active additive, join respectively the hydrogen manufacturing container from the liquid adding hole of hydrogen manufacturing container, producing the hydrogen material with activity contacts, form a kind of solid-liquid hybrid reaction system, chemical reaction takes place, produce high-purity hydrogen, the hydrogen of generation is collected by the vent valve of hydrogen manufacturing container and is utilized.In this course, also can join active additive in the hydrogen source material earlier, form solution, be poured onto in the hydrogen manufacturing container that active product hydrogen material is housed again, different hybrid modes is to the not significant difference of the process of producing hydrogen.
In this preparation method, the active molar ratio that produces hydrogen material and hydrogen source material can be 0.01-100.Suitable ratio is according to stoichiometric ratio.For example when active product hydrogen material was simple substance Zn, hydrogen source material was H 2O, its reaction formula are Zn+2H 2O → H 2+ Zn (OH) 2, the Zn of complete reaction and H 2The molar ratio of O is 1: 2.Be lower than this ratio, Zn can not complete reaction, is higher than this ratio, H 2O can not complete reaction.
Directly activity is produced the hydrogen material and contact,, all have compact oxide, in neutral medium, chemical reaction can not take place directly, produce hydrogen owing to produce the hydrogen material surface in activity with hydrogen source material.In acidity or alkaline medium,, therefore can produce hydrogen because its surperficial oxide compound is dissolved.But the use of acid, alkaline solution but come shortcomings such as environmental pollution, equipment corrosion, cost raising never has industrialization.
And among the present invention in this reaction system, added active additive, iodine (I 2), bromine (Br 2), a kind of or its mixture of iodine bromine (IBr).Discover that these additives can diffuse through the zone of oxidation on surface, are forming metal halogen compound at the interface, the water-soluble (H of this metal halogen compound height 2O), methyl alcohol (CH 3OH), ethanol (CH 3CH 2OH) in a kind of or its mixture, therefore, destroy the compact oxidation layer on metal or alloy surface, made fresh metal or alloy surface can contact hydrogen source material, produced hydrogen.This is a key of the present invention.This additive is 0.0001-1 with the active molar ratio that produces the hydrogen material.
This reaction at room temperature just can take place, and the rising temperature of reaction can quicken to produce the hydrogen process, and temperature should be controlled at below the boiling point.As-20-99 ℃.
In the process of hydrogen manufacturing, can also can under the condition of complete lucifuge, take place with the reaction soln in the solar light irradiation hydrogen manufacturing container.Irradiation of sunlight helps reducing the consumption of active additive.
Because in the present invention, gaseous product has only hydrogen, therefore, can obtain high-purity hydrogen.The productive rate of hydrogen and cost mainly depend on the amount with metal or alloy, and its speed of reaction can be controlled by the shape of mixing rate, temperature of reaction, material, the composition of hydrogen source material.And there is not extra high requirement for the purity that activity is produced the hydrogen material.This method principle innovation, equipment is simple, step is simple, material cost is very cheap, and hydrogen-producing speed is fast, is very suitable for heavy industrialization and produces hydrogen or be used for fuel cell as the original position device for producing hydrogen.A difficult problem of solved present hydrogen manufacturing, Chu Qing, fortune hydrogen, putting hydrogen has extraordinary application value, helps the development of hydrogen energy source technology.
Further specify the present invention with the comparative example by the following examples.
[embodiment 1]:
25 ℃ of room temperatures,, be positioned in the hydrogen manufacturing container of an airtight band liquid adding hole that loses light and vent valve 1 mole in Zn powder.Afterwards, 0.001 mole iodine is put into 4 moles pure H 2Among the O, form the iodine water mixed liquid, with this iodine water mixed liquid, join the hydrogen manufacturing container of putting into the Zn powder from the liquid adding hole of hydrogen manufacturing container, chemical reaction takes place, produce high-purity hydrogen, the hydrogen of generation is by the vent valve collection of hydrogen manufacturing container.The hydrogen-producing speed of this reaction is 10 milliliters/hour/gram Zn, and common property was given birth to 18 liters of hydrogen after reaction was finished.
[embodiment 2-24]
With the preparation method of embodiment 1, preparation process is identical, and different is that the kind and the relative molar ratio of active product hydrogen material, hydrogen source material, active additive are inequality.The speed that this difference causes producing hydrogen is different with the output of hydrogen, referring to table 1.The active mole number that produces the hydrogen material is decided to be 1, and molar ratio is the mol ratio of producing the hydrogen material with respect to activity in the table 1.
[embodiment 25-30]
With the preparation method of embodiment 1, preparation process is identical, and different is, the active hydrogen material that produces is simply mixed by 2 kinds or 3 kinds or 4 kinds of materials and forms, and mixing can also can join in the hydrogen manufacturing container together by mixing in advance.The chemical expression of mixture is still recently expressed by the mole of reduction all elements, according to M 1 xM 2 yM 3 zM 4 wO vIn order to show different with embodiment 1-24, be designated as M 1 x/ M 2 y/ M 3 z/ M 4 w/ O vThe kind of hydrogen source material, active additive and relative molar ratio are also inequality in addition.The speed that this difference causes producing hydrogen is different with the output of hydrogen, referring to table 1.The active mole number that produces the hydrogen material is decided to be 1, and molar ratio is the mol ratio of producing the hydrogen material with respect to activity.
[embodiment 31-93]
With the preparation method of embodiment 1, preparation process is identical, and different is, actively produces the kind of hydrogen material, hydrogen source material, active additive and molar ratio, temperature of reaction are inequality relatively.The speed that this difference causes producing hydrogen is different with the output of hydrogen, referring to table 1.The active mole number that produces the hydrogen material is decided to be 1, and molar ratio is the mol ratio of producing the hydrogen material with respect to activity.
[embodiment 94-108]
With the preparation method of embodiment 1, preparation process is identical, and different is, actively produces the kind of hydrogen material, hydrogen source material, active additive and molar ratio, temperature of reaction are inequality relatively.The speed that this difference causes producing hydrogen is different with the output of hydrogen.In the process of hydrogen manufacturing, this hydrogen manufacturing container exposes to the sun all the time and leaks under sunlight, and irradiation of sunlight helps reducing the consumption of active additive.Referring to table 1.The active mole number that produces the hydrogen material is decided to be 1, and molar ratio is the mol ratio of producing the hydrogen material with respect to activity.
Table 1: embodiment experiment condition and hydrogen-producing speed, hydrogen output.
The embodiment sequence number The active hydrogen material that produces Hydrogen source material Active additive Other reaction conditions The generation speed of hydrogen (ml/h/ g) The output of hydrogen (L)
Kind Molar ratio Kind Molar ratio
1 Zn H 2O 2 I 2 0.001 25℃ 10 20
2 Al Ethanol 1.5 I 2 0.001 25℃ 20 10
3 Mg O0.001 Methyl alcohol 2 I 2 0.001 25℃ 20 15
4 Fe H 2O 3 I 2 0.001 25℃ 50 18
5 Sn H 2O 2 I 2 0.000 1 25℃ 50 17
6 Al H 2O 0.5 I 2 0.01 25℃ 70 20
7 Al H 2O 100 I 2 0.1 25℃ 220 31
8 Al H 2O: methyl alcohol 2∶3 I 2 1 25℃ 500 29
9 Al H 2O: ethanol 1.99 ∶ 0.01 I 2 0.1 25℃ 250 27
10 Mg Ethanol: H 2O 2.99∶ 0.01 I 2 0.001 25℃ 300 16
11 Mg H 2O: ethanol: methyl alcohol ?1∶1∶1 I 2 0.001 25℃ 1200 16
12 Mg H 2O: ethanol: methyl alcohol ?4∶0.5?∶0.5 I 2 0.001 25℃ 1500 16
13 Al 2Mg H 2O ?2 I 2 0.001 25℃ 1200 14
14 AlMg H 2O ?2 I 2 0.001 25℃ 1400 13
15 Al 2Mg 3 H 2O ?2 I 2 0.001 25℃ 1500 20
16 Al 3Ti H 2O ?5 I 2 0.01 25℃ 160 24
17 MgZn 2 H 2O ?100 I 2 0.1 25℃ 2200 11
18 Mg 7Zn 3 H 2O ?2 I 2 0.001 25℃ 1400 10
19 Al 5Fe 2Zn 0.4 H 2O ?2 I 2 0.001 25℃ 1200 9
20 Zn 7Fe H 2O ?2 I 2 0.001 25℃ 50 13
21 Al 0.5Ga 0.3In 0.1Bi 0.1 H 2O ?4 I 2 0.01 25℃ 70 16
22 FeO 0.1 H 2O ?4 I 2 0.01 25℃ 80 19
23 Al 0.6Pb 0.1Bi 0.1In 0.2O 0.05 H 2O ?4 I 2 0.001 25℃ 120 14
24 Mg 2Ti H 2O ?5 I 2 0.001 25℃ 140 14
25 Al 0.5/Mg 0.5 H 2O ?5 I 2 0.001 25℃ 150 23
26 Al 0.7/Zn 0.3/O 0.05 H 2O ?5 I 2 0.01 25℃ 160 22
27 Al 0.7/Sn 0.3 H 2O ?100 I 2 0.1 25℃ 220 22
28 Mg 0.7/Fe 0.3 H 2O ?6 I 2 0.001 25℃ 1400 15
29 Al 0.7/Mg 0.1/Sn 0.1Fe 0.1 H 2O ?8 I 2 0.001 25℃ 1200 19
30 Al 0.5/Mg 0.3/Zn 0.2 H 2O ?10 I 2 0.001 25℃ 50 20
31 Mg 0.5/Zn 0.5 Ethanol ?2 Br 2/I 2 0.0/1. 0 -20℃ 800 13
32 Mg 0.5/Al 0.3/Zn 0.2 Ethanol ?2 Br 2/I 2 0.0/1. 0 30℃ 1200 16
33 Mg 0.7/Al 0.2/Zn 0.1 Ethanol ?2 Br 2/I 2 0.0/1. 0 68℃ 1400 19
34 Mg 0.8/Al 0.05/Zn 0.15 Ethanol ?2 Br 2/I 2 0.8/0. 2 -20℃ 800 20
35 Mg 0.5/Al 0.3/Zn 0.2 Ethanol ?2 Br 2/I 2 0.8/0. 2 30℃ 1600 22
36 Al 0.9/Mg 0.05/Zn 0.05 Ethanol ?2 Br 2/I 2 0.8/0. 2 62℃ 2200 26
37 Al 0.95/Mg 0.025/Zn 0.025 Ethanol ?2 Br 2/I 2 0.2/0. 8 -20℃ 400 23
38 Al 0.75/Mg 0.2/Zn 0.05 Ethanol ?2 Br 2/I 2 0.2/0. 8 30℃ 4000 22
39 Al 0.75/Fe 0.2/Zn 0.05 Ethanol ?2 BrI 0.2 65℃ 1600 23
40 Fe 0.95/Mg 0.025/Zn 0.025 Ethanol ?2 BrI 0.2 65℃ 160 19
41 Fe 0.5/Mg 0.25/Zn 0.25 Methyl alcohol ?2 BrI 0.2 -20℃ 3000 20
42 Sn 0.5/Mg 0.25/Zn 0.25 Methyl alcohol ?2 BrI 0.2 25℃ 4200 19
43 Sn 0.95/Mg 0.025/Zn 0.025 Methyl alcohol ?2 BrI 0.2 60℃ 1600 14
44 Fe 0.5/Mg 0.25/Zn 0.25 Methyl alcohol ?2 BrI 0.2 -20℃ 280 14
45 Sn 0.5/Al 0.25/Zn 0.25 Methyl alcohol ?2 BrI 0.2 25℃ 350 19
46 Sn 0.95/Al 0.025/Zn 0.025 Methyl alcohol ?2 BrI 0.2 60℃ 150 18
47 Mg 0.7/Al 0.2/Zn 0.1 Methyl alcohol ?2 BrI 0.2 -20℃ 9000 21
48 Mg 0.8/Al 0.05/Zn 0.15 Methyl alcohol ?2 BrI 0.2 25℃ 5000 23
49 Mg 0.5/Al 0.3/Zn 0.2 Methyl alcohol ?2 BrI 0.4 60℃ 4000 22
50 Al 0.9/Mg 0.05/Zn 0.05 Methyl alcohol ?2 BrI 0.4 -10℃ 3000 20
51 Al 0.95/Mg 0.025/Zn 0.025 Methyl alcohol ?2 BrI 0.4 25℃ 4200 23
52 Al 0.75/Mg 0.2/Zn 0.05 Methyl alcohol ?2 BrI 0.4 60℃ 1600 22
53 Al 0.75/Fe 0.2/Zn 0.05 Ethanol ?2 BrI 0.4 -20℃ 2800 21
54 Fe 0.95/Mg 0.025/Zn 0.025 Ethanol ?2 BrI 0.4 30℃ 3500 16
55 Fe 0.5/Mg 0.25/Zn 0.25 Ethanol ?2 BrI 0.4 68℃ 1500 16
56 Sn 0.5/Mg 0.25/Zn 0.25 Ethanol ?2 BrI 0.4 -20℃ 3000 14
57 Sn 0.95/Mg 0.025/Zn 0.025 Ethanol ?2 BrI 0.4 30℃ 4200 13
58 Fe 0.5/Mg 0.25/Zn 0.25 Ethanol ?2 BrI 0.4 60℃ 1600 12
59 Sn 0.5/Al 0.25/Zn 0.25 Ethanol ?2 BrI 0.4 -20℃ 3000 12
60 Sn 0.95/Al 0.025/Zn 0.025 Ethanol ?2 Br/I 0.2/0. 8 30℃ 4200 11
61 Mg H 2O 2 Br/I 0.2/0. 8 60℃ 1600 17
62 Al 0.5/Mg 0.5 H 2O 2 I 2 0.1 25℃ 1800 26
63 Mg H 2O 2 Br 2/I 2/ BrI 0.05/0 .05/0. 05 20℃ 3000 16
64 Mg H 2O 2 Br 2/I 2/ BrI 0.005/ 0.005/ 0.005 25℃ 4200 16
65 Mg 0.5/Al 0.3/Zn 0.2 H 2O 2 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 60℃ 1600 17
66 Mg 0.5/Al 0.3/Zn 0.2 H 2O 2 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 20℃ 2800 16
67 Mg 0.5/Al 0.3/Zn 0.2 H 2O 2 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 25℃ 3500 16
68 Mg 0.5/Al 0.3/Zn 0.2 H 2O 2 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 60℃ 1500 16
69 Mg 0.5/Al 0.3/Zn 0.2 H 2O 2 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 -20℃ 3200 14
70 Mg 0.5/Al 0.3/Zn 0.2 H 2O 4 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 25℃ 4200 13
71 Al 0.9/Mg 0.05 H 2O 4 Br 2/I 2/ BrI 0.001/ 0.01/0 .001 60℃ 5000 18
72 Al 0.95/Mg 0.025/Zn 0.025 H 2O 4 I 2 0.1 10℃ 300 12
73 Al 0.75/Mg 0.2/Zn 0.05 H 2O 4 I 2 0.1 25℃ 4200 11
74 Al 0.75/Fe 0.2/Zn 0.05 H 2O 4 I 2 0.1 60℃ 6600 17
75 Al 0.9/Mg 0.05/Zn 0.05 H 2O 4 I 2 0.1 20℃ 2800 16
76 Al 0.95/Mg 0.025/Zn 0.025 H 2O 4 I 2 0.1 30℃ 3500 16
77 Al 0.75/Mg 0.2/Zn 0.05 H 2O 4 I 2 0.1 68℃ 1500 16
78 Al 0.75/Fe 0.2/Zn 0.05 H 2O 4 I 2 0.1 20℃ 3000 14
78 Mg H 2O 4 I 2 0.1 30℃ 2200 13
79 Al 0.9/Mg 0.05/Zn 0.05 H 2O 4 I 2 0.1 62℃ 4600 12
80 Al 0.95/Mg 0.025/Zn 0.025 H 2O 4 I 2 0.1 20℃ 3000 12
81 Al 0.75/Mg 0.2/Zn 0.05 H 2O 4 I 2 0.1 30℃ 4200 11
82 Al 0.75/Fe 0.2/Zn 0.05 H 2O 4 I 2 0.1 99℃ 1600 17
84 Mg H 2O 4 I 2 0.1 20℃ 1600 16
85 Mg H 2O 4 I 2 0.1 25℃ 2400 16
86 Mg H 2O 4 I 2 0.1 60℃ 4500 16
87 Fe 0.5/Mg 0.25/Zn 0.25 H 2O 4 I 2 0.1 20℃ 2800 14
88 Sn 0.5/Al 0.25/Zn 0.25 H 2O 4 I 2 0.1 25℃ 1500 13
89 Sn 0.95/Al 0.025/Zn 0.025 H 2O 4 I 2 0.1 60℃ 5500 12
90 Mg 0.7/Al 0.2/Zn 0.1 H 2O 4 I 2 0.1 20℃ 9000 12
91 Mg 0.8/Al 0.05/Zn 0.15 H 2O 4 I 2 0.1 25℃ 4200 11
92 Al H 2O 10 I 2 0.1 60℃ 160 17
93 Sn H 2O 10 I 2 0.1 10℃ 300 12
94 Fe H 2O 10 I 2 0.01 25℃ 42 11
95 Al 0.9/Mg 0.05/Zn 0.05 H 2O 4 I 2 0.01 20℃ 2800 16
96 Al 0.95/Mg 0.025/Zn 0.025 H 2O 4 I 2 0.01 30℃ 3500 16
97 Al 0.75/Mg 0.2/Zn 0.05 H 2O 4 I 2 0.01 68℃ 1500 16
98 Al 0.75/Fe 0.2/Zn 0.05 H 2O 4 I 2 0.01 20℃ 3000 14
99 Mg H 2O 4 I 2 0.01 30℃ 2200 13
101 Al 0.9/Mg 0.05/Zn 0.05 H 2O 4 I 2 0.01 62℃ 4600 12
102 Al 0.95/Mg 0.025/Zn 0.025 H 2O 4 I 2 0.01 20℃ 3000 12
103 Al 0.75/Mg 0.2/Zn 0.05 H 2O 4 I 2 0.01 30℃ 4200 11
104 Al 0.75/Fe 0.2/Zn 0.05 H 2O 4 I 2 0.01 99℃ 1600 17
105 Mg H 2O 4 I 2 0.01 20℃ 1600 16
106 Mg H 2O 4 I 2 0.01 25℃ 2400 16
107 Mg H 2O 4 I 2 0.01 60℃ 4500 16
108 Fe 0.5/Mg 0.25/Zn 0.25 H 2O 4 I 2 0.01 20℃ 2800 14

Claims (8)

1. a hydrogen preparation method is characterized in that, this method may further comprise the steps:
(1) selects M 1 xM 2 yM 3 zM 4 wO vA kind of or its mixture of metal or alloy produces the hydrogen material as activity;
In the formula:
M 1Be selected from Mg, Al, Zn, Fe, the Sn element,
M 2, M 3, M 4Be selected from Mg, Al, Zn, Fe, Sn, Ga, In, Bi, Pb, Ti element
O is an oxygen element,
X, y, z, w, v are the atomic molar umber, 0.5≤x≤1,0≤(y, z, w)≤0.5 and X+y+z+w=1; 0≤v≤0.1, M 1≠ M 2≠ M 3≠ M 4
(2) select water, methyl alcohol, alcoholic acid is a kind of or its mixture as hydrogen source material;
(3) select a kind of or its mixture of iodine, bromine, iodine bromine as active additive;
Activity is produced the hydrogen material place an airtight band liquid adding hole and the hydrogen manufacturing container of vent valve, with a kind of active additive and a kind of hydrogen source material, add from the liquid adding hole of hydrogen manufacturing container, producing the hydrogen material with activity contacts, form a kind of solid-liquid hybrid reaction system, chemical reaction takes place, produce high-purity hydrogen, the hydrogen of generation is collected by the vent valve of hydrogen manufacturing container and is utilized.
2. hydrogen preparation method as claimed in claim 1 is characterized in that, described metal or alloy is powder, piece or porous material.
3. hydrogen preparation method as claimed in claim 1 is characterized in that described metal or alloy is a silk.
4. hydrogen preparation method as claimed in claim 1 is characterized in that described metal or alloy is a line.
5. hydrogen preparation method as claimed in claim 1 is characterized in that, described metal or alloy is a rod.
6. hydrogen preparation method as claimed in claim 1 is characterized in that, the active molar ratio that produces hydrogen material and hydrogen source material is 0.5-100, and active additive is 0.0001-1 with active mol ratio of producing the hydrogen material.
7. hydrogen preparation method as claimed in claim 1 is characterized in that, in the process of hydrogen manufacturing, and the temperature of control hydrogen manufacturing container, temperature range is at-20-99 ℃.
8. hydrogen preparation method as claimed in claim 1 is characterized in that, in hydrogen production process, with the reaction soln in the solar light irradiation hydrogen manufacturing container, or takes place under the condition of complete lucifuge.
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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
CN109988944A (en) * 2017-12-29 2019-07-09 吉林大学 A kind of hydrolytic hydrogen production aluminium alloy and the method for improving aluminium alloy hydrogen production rate
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范美强等.铝水反应制氢技术.《电源技术》.2007,第31卷(第7期),实验,表1. *

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