CN110327936A - A kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material and preparation method thereof - Google Patents
A kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material and preparation method thereof Download PDFInfo
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- CN110327936A CN110327936A CN201910610972.5A CN201910610972A CN110327936A CN 110327936 A CN110327936 A CN 110327936A CN 201910610972 A CN201910610972 A CN 201910610972A CN 110327936 A CN110327936 A CN 110327936A
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Abstract
The invention discloses a kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material and preparation method thereof, chooses metal MAG block and magnesium nickel intermediate alloy proportion in SF6+CO2Mixed atmosphere protects lower melting to prepare rich magnesium alloy cast ingot.Rich magnesium master alloyed powder is prepared by high-energy ball-milling process, short time high-energy ball milling surface catalysis technique is protected by argon gas, in rich magnesium alloying pellet surface inserting EG-SnO2Nano material does the compound material of going out of rich magnesium that surface catalysis is modified, and acquisition nano surface is modified.The activity on rich magnesium alloying pellet surface is obviously improved；And nano surface catalyst can Preferential adsorption active gases molecule, the effectively formation of inhibition magnesium-nickel alloy particle surface MgO passivation layer；In sequential hydrolysis hydrogen production process, the nano surface catalyst of layer structure and tubular structure can effectively destroy hydrolysate Mg (OH)2The integrality of colloidal film promotes the quick and complete hydrolysis in a short time of magnesium-nickel alloy particle, significantly improves rich magnesium alloy and initially produces hydrogen dynamics and improve the hydrogen manufacturing yield of rich magnesium alloy.
Description
Technical field
The invention belongs to technical field of metal material, and in particular to a kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni
Produce hydrogen material and preparation method thereof.
Background technique
Energy crisis and environmental pollution force people to seek new sustainable green energy resource to push future life.Energy road
The development of diameter is considered as coal (C) → oil (- CH2) → natural gas (CH4) → hydrogen (H2).The C/H ratio decline of fuel shows energy
More, CO2 emissions are less.With solar energy, wind energy, tide energy, the new energy such as water energy are corresponding, and hydrogen energy source is because of its kind
Class is various, and energy storage density is high, can be recycled with zero-emission and as trend of the times.Therefore, promote the utilization of hydrogen and establish hydrogen economy
As main and urgent science and industry challenge.
Nowadays, the extensive use of Hydrogen Energy in practice is still largely by H2Generation and H2The limit of storage problem
System.In H2Storage aspect has done many effort, stores H2Main trend be the solid-state hydrogen storage method occurred in recent years.Though
It so has made some progress, but still there is an urgent need to low cost, the solid-state H of high capacity and safety for amount transport2Storage material.
In addition, research and development low energy consumption, inexpensive efficient H2Generation technology is extremely urgent.Nowadays, the H largely used2Main source
In gas reforming technology.Although zero-emission H2It is to be produced by gas reforming mode, but a large amount of greenhouse gases CO2And one
Other a little pernicious gases can also release.More seriously, due to the raw material for gas reforming, energy crisis and environment
The pressure of pollution is not responded actively.
H is generated by water currently, proposing2Production hydrogen methods.Main water hydrogen production method can be divided into three classes, that is, be electrolysed
Water, photocatalytic water and alloy hydrolysis water.A large amount of energy consumption and shortage catalyst are the main bottlenecks of electrolysis water.Expensive is efficient
Catalyst seriously prevents a large amount of hydrogen generated by photocatalytic water.Develop facing challenges, researcher to cope with Hydrogen Energy
It must try one's best and seek new H2Storage and H2Production strategy.With realizing above-mentioned real-time H in the near future2It generates, in advance
Phase H2Immediately the case where then using immediately is generated to be seen everywhere.By hydrolysis in water, using with high activity
Alloy produces hydrogen.High activity metal can react with water and replace a large amount of H atoms from water.Solid hydrogen hair based on this principle
Raw device can be to avoid H2Storage and transport, and a possibility that use can be provided for the hydrogen of various regions.However, for passing through
Hydrolysis generates H2Metal material it is unsatisfactory.It is reported that active acieral and magnesium base alloy generate H for hydrolyzing2,
It has many advantages that, such as abundant raw material, generated energy is high, and more economical, system/device is than other water H2Generation method is simple.It is living
Property acieral there is high theory H2Generative capacity, and the by-product lye of hydrolysis can be used for sewage treatment or other works
Industry.However, the hydrolytic process of high-purity Al and acieral be proved to by neutral water for generating H2High activity
Limitation.The intrinsic low surface-active of Al alloy is attributed to surface A l2O3The formation of passivation layer, and this oxide layer is usually continuous
And fine and close.In order to accelerate to hydrolyze H2Acid or alkaline solution is directly added into dissolve the surface on Al alloy by generating process
Passivation layer.Increase H in acid medium2It generates, cost is that risk of environmental pollution rises.Therefore, the certainly living of acieral is improved
Property, avoid the formation of continuous dense oxide layer Al2O3, realize that the hydrolysis of neutral aqueous solution is the main task of researcher.
Mg is to the H in neutral solution2It generates tool to play a very important role, because its advantage includes high theory H2Generative capacity
(8.2wt.%), high electrochemical activity (2.37VSHE) and lightweight (1.74gcm-3).Hydrogen material property, people are produced to improve magnesium-based
Often through addition active metallic element regulation magnesium base alloy activity or by high-energy-milling refining alloy tissue, increase ratio
Surface area improves its dynamic characteristic of hydrogen production.But often surface easily forms the passivation layers such as MgO to alloy, reduces alloy surface
Activity, it is suppressed that H2The adsorption and mass transfer of O keeps production hydrogen initial rate especially slow.In addition, while magnesium alloy hydrolysis is processed
It is formed Mg (OH)2Colloid product, product successively wrap up, it is suppressed that the entrance of subsequent medium makes alloy can not complete hydrolysis production
Hydrogen, ultimate yield are lower.In view of above-mentioned two aspects reason, developing high-yield quick rate magnesium-based and producing hydrogen material is the weight studied from now on
Point.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the technical problem to be solved by the present invention is that providing a kind of EG-SnO2@
The nano combined catalyzing hydrolysis of Mg-Ni produces hydrogen material and preparation method thereof, by surface in short-term high-energy-milling in rich magnesium alloy
Particle surface its intercalated layered EG or tubulose SnO2, magnesium alloy particles oxide layer can be effectively suppressed and formed, improve material surface
Activity；The nano material for being embedded in surface can effectively inhibit colloid Mg (OH) in the production hydrogen later period2The integrality of film promotes material and produces
The diffusion transport characteristic of hydrogen later period medium is obviously improved the hydrogen manufacturing yield of magnesium base alloy.
The invention adopts the following technical scheme:
A kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material, EG-SnO2EG- in@Mg10Ni composite material
SnO20~20wt.% is accounted for, remaining is Mg-10wt.%Ni alloy.
Specifically, EG-SnO2Middle EG:SnO2=(1~2): (2~1), in Mg-Ni alloy, nickel 10wt.%.
Another technical solution of the invention is a kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material
Preparation method, comprising the following steps:
S1, the metal MAG block for choosing purity >=99.8% and 30% magnesium nickel intermediate alloy carry out ingredient；
The step S1 MAG block prepared and magnesium nickel intermediate alloy block are put into the graphite earthenware dried in advance by S2, matrix alloy preparation
In crucible, uniform rich magnesium alloy melt is prepared in heating stirring, is continued to heat up and be stirred, and is cast after alloy block all fusing
Into the steel die preheated in advance, it is air-cooled to room temperature, obtains magnesium rich magnesium alloy cast ingot；
S3, the rich magnesium alloy cast ingot that step S2 is obtained is placed in the closed ball milling tank of argon gas protection, passes through high energy vibration
Ball mill ball milling hits constantly refinement crystal grain and obtains alloy powder；By obtained alloyed powder and EG-SnO2Ball grinder is added simultaneously
High-energy ball milling in short-term is carried out, EG-SnO is obtained2The nano combined production hydrogen material of@Mg10Ni base.
Specifically, magnesium adds the scaling loss of 2~6wt.% in step S1.
Specifically, graphite crucible is in SF in step S26+CO2720~820 DEG C are heated under mixed atmosphere protection, 200~
400rap/min 20~40min of mechanical stirring obtains uniform rich magnesium alloy melt.
Specifically, rich magnesium alloy melt being continuously heating to 900~950 DEG C in step S2, and keep the temperature 15~30min, being melted
200~400rap/min mechanical stirring is mixed in body insulating process.
Specifically, the preheating temperature of steel die is 240~300 DEG C in step S2.
Specifically, obtained rich magnesium alloy cast ingot is placed in the closed ball milling tank of argon gas protection, ratio of grinding media to material in step S3
(10~30): (1), 2~6h of Ball-milling Time, drum's speed of rotation 875rap/min obtain alloy powder.
Further, in step S3, alloyed powder and EG-SnO2High-purity argon gas protection under in short-term high-energy ball milling 10~
30min。
Specifically, in step S3, by obtained alloyed powder and EG-SnO2Ball grinder, EG-SnO are added simultaneously2Account for 0~
20wt.%, EG:SnO2=(1~2): (2~1).
Compared with prior art, the present invention at least has the advantages that
A kind of EG-SnO of the present invention2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material, by EG and SnO2High-specific surface area
High activity feature effectively inhibits side effect of the active gases molecule for rich magnesium alloying pellet surface, it is suppressed that surface MgO and
Mg(OH)2The formation of passivation layer significantly improves the surface-active of material.In addition, the synusia gap of EG and SnO2Tubulose knot
Structure can crack Mg (OH) in the production hydrogen later period2The integrality of surface colloid layer enters inside alloy for medium and provides convenient lead to
Road promotes complete hydrolysis inside particle, improves the hydrolytic hydrogen production yield of rich magnesium material, improve the utilization rate of material, obtains
It is avoided while rapid, high volume hydrogen and inhales hydrogen release repeatedly and cause the excessive dusting of particle, and then cause mass-and heat-transfer difficulty etc. to ask
Topic.
A kind of EG-SnO of the present invention2The nano combined catalyzing hydrolysis of@Mg-Ni produces the preparation method of hydrogen material, influences initially to produce
Alloy sample surfactant surface mass transport process before hydrogen is destroyed and produces hydrogen later period surface Mg (OH)2Colloid layer integrality accelerates to produce
Hydrogen later period Medium Diffusion process of osmosis.
Further, pure metallic nickel is replaced using Mg-30wt.%Ni intermediate alloy, when can effectively reduce alloy melting
Temperature effectively reduces metal magnesium loss, so that the ingredient accuracy of molten alloy be effectively ensured.
Further, uniform Mg-10wt.%Ni alloy melt can guarantee the equal of alloy structure and ingredient in process of setting
Even property can fully ensure that transition metal nickel Dispersed precipitate, in the Mg10Ni alloy obtained after solidification, Mg2Ni interphase is uniformly divided
Cloth, can Effective Regulation alloy hydrolysis produce hydrogen behavior.
Further, magnesium-nickel alloy melt heating stirring can promote strongly ingredient and temperature to be uniformly distributed, and shorten and obtain
In the even magnesium-nickel alloy melt period, improve production efficiency.
Further, when steel die does not preheat, due to the excessive temperature difference, on the one hand, can be generated to high-temperature fusant very big
Thermal shock, easily formation thermal stress, promote alloy to form a large amount of fire checks, to cause biggish alloy brittleness, be convenient for
Later period ball powder-grinding；On the other hand, the temperature difference being added to will lead to big degree of supercooling, promotes alloy to form thin crystal grain, is conducive to
Hydrolysis produces the medium transmission in hydrogen reaction.
Further, as cast condition Mg-10wt.%Ni bianry alloy ingot casting be placed in argon gas protection closed ball milling tank in ball milling can
Pollution of the reactive atmosphere for alloying pellet in mechanical milling process is avoided, clean surface high-activity magnesium nickel alloy particles are easily obtained,
Condition is provided for fast hydrolyzing.
Further, the EG-SnO2 of ball milling addition in short-term is to be embedded in high-activity nano on Mg10Ni alloying pellet surface
Layered catalyst and nanotube-shaped catalyst, by bigger serface provided by surface catalyst stratiform and tubular structure, height
Active gap promotes the surface-active of magnesium-nickel alloy particle, improves medium transmission process, inhibits the formation of MgO passivation layer and destruction
The colloid Mg (OH) that surface is formed2The integrality of film promotes hydrolysis dynamics and hydrogen manufacturing yield.
Further, high-energy ball milling can be by grinding in Process During High Energy Ball Milling in short-term in short-term by magnesium-nickel alloy particle and EG-SnO2
The mechanism of ball, make added catalyst even dispersion is embedded in rich magnesium alloying pellet surface, in hydrolytic process sufficiently
It plays a role.If Ball-milling Time is too long, the stratiform or tubulose micro-structure of surface catalyst can be destroyed, catalytic effect is influenced.
It initially produces hydrogen dynamics in conclusion the present invention significantly improves rich magnesium alloy and improves the hydrogen manufacturing production of rich magnesium alloy
Rate.
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Detailed description of the invention
Fig. 1 is EG prepared by the present invention and SnO2Microstructure morphology, wherein (a) is SnO2Micro-structure；It (b) is the micro- knot of EG
Structure；
Fig. 2 is EG-SnO of the present invention2The nano combined production hydrogen-time graph for producing hydrogen material of@Mg10Ni, wherein (a) is
(0wt.%) EG-SnO260s produces hydrogen kinetic curve before@Mg10Ni；It (b) is (5wt.%) EG-SnO260s produces hydrogen before@Mg10Ni
Kinetic curve.
Specific embodiment
The present invention provides a kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material, i.e. EG-SnO2@Mg10Ni
Composite material, wherein EG-SnO2Account for 0~20wt.%, EG:SnO2=(1~2): (2~1), remaining is Mg-10wt.%Ni conjunction
Gold.
For hydrolysis produces hydrogen alloy: hydrogen-producing speed, production hydrogen capacity and hydrogen manufacturing yield are the performance parameters paid close attention to.
The differences such as different-alloy micro-structure, activating agent surface state show different hydrolysis hydrogen-producing characteristics.Pure magnesium hydrolysis produces the reason of hydrogen
By capacity in 25 DEG C of about 1000mL/min, but because pure MAG block body alloy specific surface area is small, diffusion admittance is long, and surface exists
Oxide passivation layer is often difficult saturation and produces hydrogen, so the pure magnesium hydrogen output of block is generally very low.Hydrogen-producing speed and hydrogen manufacturing yield because
Medium, temperature, material size dimension etc. are different and different.
Simple alloying means only improve the speed and capacity for producing hydrogen, smaller to hydrogen manufacturing yield mailbox, and initial
Hydrolysis rate also has received the influence of surface passivation layer, it can be seen that, surface characteristic significantly affects the hydrogen manufacturing characteristic of alloy.Using
The compound production hydrogen material of novel nano prepared by the composite modified modification of nano surface provided by the present invention, both ensure that it is fast just
Beginning and process hydrogen-producing speed, in turn ensure high hydrogen manufacturing yield, have been obviously improved the utilization rate of material, avoid the wave of material
Take.
A kind of EG-SnO of the present invention2The nano combined catalyzing hydrolysis of@Mg-Ni produces the preparation method of hydrogen material, including following step
It is rapid:
S1, alloying ingredient
The metal MAG block and 30% magnesium nickel intermediate alloy for choosing purity >=99.8% are 10wt.% by nickel content, remaining is
Magnesium proportion, it is contemplated that scaling loss, magnesium add the scaling loss of 2~6wt.%；
S2, matrix alloy preparation
The MAG block weighed up and magnesium nickel intermediate alloy block are put into the graphite crucible dried in advance, in SF6+CO2Mixed atmosphere
720~820 DEG C are heated under protection, 200~400rap/min, 20~40min of mechanical stirring obtains uniform rich magnesium alloy melt,
Alloy melt is continuously heating to 900~950 DEG C, and keeps the temperature 15~30min.200~400rap/ is mixed in melt insulating process
Min mechanical stirring, casting is air-cooled to room temperature into the steel die for being preheated to 300 DEG C in advance after alloy block all fusing,
Obtain magnesium rich magnesium alloy cast ingot；
S3, nano surface modification
Obtained rich magnesium alloy cast ingot is placed in the closed ball milling tank of argon gas protection, passes through high-energy ball milling machine ball milling
Constantly refinement crystal grain is hit, ratio of grinding media to material (10~30): (1), 2~6h of Ball-milling Time, drum's speed of rotation 875rap/min are closed
Bronze material, by obtained alloyed powder and EG-SnO2Ball grinder is added simultaneously, wherein EG-SnO2Account for 0~20wt.%, EG:SnO2=
(1~2): (2~1), 10~30min of high-energy ball milling in short-term under high-purity argon gas protection realize that surface recombination is nano-modified, obtain
EG-SnO2The nano combined production hydrogen material of@Mg10Ni base.
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.The present invention being described and shown in usually here in attached drawing is real
The component for applying example can be arranged and be designed by a variety of different configurations.Therefore, below to the present invention provided in the accompanying drawings
The detailed description of embodiment be not intended to limit the range of claimed invention, but be merely representative of of the invention selected
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
EG-SnO of the present invention2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material by EG-SnO2And Mg-10wt.%
Ni rich magnesium composition of alloy, wherein EG-SnO2Account for 0wt.%, EG:SnO2=1:2, remaining is Mg-10wt.%Ni alloy.
Step 1, alloying ingredient
The metal MAG block and 30% magnesium nickel intermediate alloy for choosing purity >=99.8% are 10wt.% by nickel content, remaining is
Magnesium proportion, it is contemplated that scaling loss, magnesium add the scaling loss of 2wt.%.
Step 2, prepared by matrix alloy
The MAG block weighed up and magnesium nickel intermediate alloy block are put into the graphite crucible dried in advance, in SF6+CO2Mixed atmosphere
720 DEG C are heated under protection, 200rap/min mechanical stirring 20min obtains uniform rich magnesium alloy melt, alloy melt is continued
900 DEG C are warming up to, and keeps the temperature 15min.200rap/min mechanical stirring is mixed in melt insulating process, it is all molten to alloy block
Casting is air-cooled to room temperature, obtains magnesium rich magnesium alloy cast ingot into the steel die for being preheated to 240 DEG C in advance after change.
Step 3, nano surface is modified
Obtained rich magnesium alloy cast ingot is placed in the closed ball milling tank of argon gas protection, passes through high-energy ball milling machine ball milling
It hits constantly refinement crystal grain, ratio of grinding media to material 10:1, Ball-milling Time 2h, drum's speed of rotation 875rap/min and obtains alloy powder, will
The alloyed powder and 0wt.%EG-SnO arrived2Ball grinder is added simultaneously, wherein EG:SnO2=1:2, under high-purity argon gas protection in short-term
High-energy ball milling 10min realizes that surface recombination is nano-modified, obtains (0wt.%) EG-SnO2The nano combined production hydrogen material of@Mg10Ni
Material.
Embodiment 2
EG-SnO of the present invention2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material by EG-SnO2And Mg-10wt.%
Ni rich magnesium composition of alloy, wherein EG-SnO2Account for 10wt.%, EG:SnO2=1:1, remaining is Mg-10wt.%Ni alloy.
Step 1, alloying ingredient
The metal MAG block and 30% magnesium nickel intermediate alloy for choosing purity >=99.8% are 10wt.% by nickel content, remaining is
Magnesium proportion, it is contemplated that scaling loss, magnesium add the scaling loss of 4wt.%.
Step 2, prepared by matrix alloy
The MAG block weighed up and magnesium nickel intermediate alloy block are put into the graphite crucible dried in advance, in SF6+CO2Mixed atmosphere
770 DEG C are heated under protection, 300rap/min mechanical stirring 30min obtains uniform rich magnesium alloy melt, alloy melt is continued
925 DEG C are warming up to, and keeps the temperature 22.5min.300rap/min mechanical stirring is mixed in melt insulating process, to alloy block whole
Casting is air-cooled to room temperature, obtains magnesium rich magnesium alloy cast ingot into the steel die for being preheated to 270 DEG C in advance after fusing.
Step 3, nano surface is modified
Obtained rich magnesium alloy cast ingot is placed in the closed ball milling tank of argon gas protection, passes through high-energy ball milling machine ball milling
It hits constantly refinement crystal grain, ratio of grinding media to material 20:1, Ball-milling Time 4h, drum's speed of rotation 875rap/min and obtains alloy powder, will
The alloyed powder and 10wt.%EG-SnO arrived2Ball grinder is added simultaneously, wherein EG:SnO2=1:1, under high-purity argon gas protection in short-term
High-energy ball milling 20min realizes that surface recombination is nano-modified, obtains (10wt.%) EG-SnO2The nano combined production hydrogen material of@Mg10Ni
Material.
Embodiment 3
EG-SnO of the present invention2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material by EG-SnO2And Mg-10wt.%
Ni rich magnesium composition of alloy, wherein EG-SnO2Account for 0~20wt%, EG:SnO2=1:1, remaining is Mg-10wt.%Ni alloy.
Step 1, alloying ingredient
The metal MAG block and 30% magnesium nickel intermediate alloy for choosing purity >=99.8% are 10wt.% by nickel content, remaining is
Magnesium proportion, it is contemplated that scaling loss, magnesium add the scaling loss of 6wt.%.
Step 2, prepared by matrix alloy
The MAG block weighed up and magnesium nickel intermediate alloy block are put into the graphite crucible dried in advance, in SF6+CO2Mixed atmosphere
820 DEG C are heated under protection, 400rap/min mechanical stirring 40min obtains uniform rich magnesium alloy melt, alloy melt is continued
950 DEG C are warming up to, and keeps the temperature 30min.400rap/min mechanical stirring is mixed in melt insulating process, it is all molten to alloy block
Casting is air-cooled to room temperature, obtains magnesium rich magnesium alloy cast ingot into the steel die for being preheated to 300 DEG C in advance after change.
Step 3, nano surface is modified
Obtained rich magnesium alloy cast ingot is placed in the closed ball milling tank of argon gas protection, passes through high-energy ball milling machine ball milling
It hits constantly refinement crystal grain, ratio of grinding media to material 30:1, Ball-milling Time 6h, drum's speed of rotation 875rap/min and obtains alloy powder, will
The alloyed powder and 20wt.%EG-SnO arrived2Ball grinder is added simultaneously, wherein EG:SnO2=2:1, under high-purity argon gas protection in short-term
High-energy ball milling 30min realizes that surface recombination is nano-modified, obtains (20wt.%) EG-SnO2The nano combined production hydrogen material of@Mg10Ni
Material.
The rich magnesium alloying component and even tissue degree that different technical parameters obtain are different；The richness of different ball-milling technology preparations
The distribution of magnesium alloy particles size and specific surface area are different；Different surfaces catalyst loading, different catalysts composition and not
With surface catalysis technological parameter, so that catalyst is different in the degree that rich magnesium alloying pellet surface is distributed, to produce hydrogen in hydrolysis
Make material surface active in the process, the integrality of mass transfer rate, surface passivated membrane and surface colloid Product Films has differences, thus
It obtains the different degrees of hydrolysis of different rates and produces hydrogen material, meet the application demand of different occasions.
Hydrogen advantage is produced to retain magnesium base alloy large capacity, the present invention selects rich magnesium alloy as matrix modification alloy, herein
On the basis of, it is modified by nano surface, improves initial production hydrogen activation characteristic and the later period produces hydrogen diffusion mass transfer process, obtain high system
Hydrogen yield.The present invention is based on microalloying Mg-10wt.%Ni bianry alloys, are added by high-energy ball milling surface catalysis technology in short-term
Add EG-SnO2Nano hybridization body prepares EG-SnO2The compound production hydrogen material of@Mg10Ni is promoted significant on the basis of initial hydrogen-producing speed
Improve the diffusion mass transfer process for producing the hydrogen later period, promote rich magnesium alloy complete hydrolysis, obtain high yield, while obtaining hydrogen energy source
The waste for reducing material, meets application request.
Referring to Fig. 1, Fig. 1 (a) is the microstructure appearance figure of nanocatalyst EG, it can be seen from the figure that EG is in synusia
Shape structure, there are gaps between piece and piece, produce hydrogen process always for medium and H2Quickly transmission.Fig. 1 (b) is nanocatalyst
SnO2Microstructure appearance figure, it can be seen that SnO2Typical tubular nanostructures are presented, there is great surface area.Above-mentioned two
Kind of catalyst is added in rich magnesium alloy material, is producing hydrogen initial stage, can Preferential adsorption active impurity gas molecule, inhibit rich magnesium to close
Gold particle surface forms continuous N gO2Layer, production hydrogen later period can destroy to form Mg (OH)2The continuity of layer passes for later period Medium Diffusion
Defeated offer easy access, promotes alloying pellet complete hydrolysis, it is ensured that high hydrogen manufacturing yield.
Referring to Fig. 2, Fig. 2 (a) and Fig. 2 (b) is (0wt.%) EG-SnO2@Mg10Ni and (5wt.%) EG-SnO2@
The production hydrogen kinetic curve of 60s before the nano-modified compound production hydrogen material of Mg10Ni, from figure 2 it can be seen that EG-SnO2It is compound to receive
The hydrolysis of the modified rich magnesium alloy material of rice produces hydrogen initial driving force characteristic and is significantly improved, and reason is nano combined
It is modified, it is added to the nano material large specific surface area on alloying pellet surface, Preferential adsorption active impurity gas molecule, certain journey
Degree inhibits the formation of surface passivation layer, improves rich magnesium granule surface activity.Hydrolysis initial stage nano surface additive can be a large amount of
Adsorbed water molecule comes into full contact with hydrone and alloying pellet, thus fast hydrolyzing hydrogen manufacturing.
The above content is merely illustrative of the invention's technical idea, and this does not limit the scope of protection of the present invention, all to press
According to technical idea proposed by the present invention, any changes made on the basis of the technical scheme each falls within claims of the present invention
Protection scope within.
Claims (10)
1. a kind of EG-SnO2The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material, which is characterized in that EG-SnO2@Mg10Ni is compound
EG-SnO in material20~20wt.% is accounted for, remaining is Mg-10wt.%Ni alloy.
2. EG-SnO according to claim 12The nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material, which is characterized in that EG-
SnO2Middle EG:SnO2=(1~2): (2~1), in Mg-Ni alloy, nickel 10wt.%.
3. a kind of prepare EG-SnO as claimed in claim 1 or 22The method that the nano combined catalyzing hydrolysis of@Mg-Ni produces hydrogen material, it is special
Sign is, comprising the following steps:
S1, the metal MAG block for choosing purity >=99.8% and 30% magnesium nickel intermediate alloy carry out ingredient；
The step S1 MAG block prepared and magnesium nickel intermediate alloy block are put into the graphite crucible dried in advance by S2, matrix alloy preparation
In, uniform rich magnesium alloy melt is prepared in heating stirring, continue to heat up and stir, after alloy block all fusing after cast to
In the steel die preheated in advance, it is air-cooled to room temperature, obtains magnesium rich magnesium alloy cast ingot；
S3, the rich magnesium alloy cast ingot that step S2 is obtained is placed in the closed ball milling tank of argon gas protection, passes through high-energy ball milling
Machine ball milling hits constantly refinement crystal grain and obtains alloy powder；By obtained alloyed powder and EG-SnO2Ball grinder progress is added simultaneously
High-energy ball milling in short-term obtains EG-SnO2The nano combined production hydrogen material of@Mg10Ni base.
4. preparation method according to claim 3, which is characterized in that in step S1, magnesium adds the scaling loss of 2~6wt.%.
5. preparation method according to claim 3, which is characterized in that in step S2, graphite crucible is in SF6+CO2Gaseous mixture
720~820 DEG C, 200~400rap/min, 20~40min of mechanical stirring are heated under atmosphere protection, it is molten to obtain uniform rich magnesium alloy
Body.
6. preparation method according to claim 3, which is characterized in that in step S2, rich magnesium alloy melt is continued to heat up
To 900~950 DEG C, and 15~30min is kept the temperature, is mixed with 200~400rap/min mechanical stirring in melt insulating process.
7. preparation method according to claim 3, which is characterized in that in step S2, the preheating temperature of steel die is 240
~300 DEG C.
8. preparation method according to claim 3, which is characterized in that in step S3, obtained rich magnesium alloy cast ingot is set
In the closed ball milling tank of argon gas protection, ratio of grinding media to material (10~30): (1), and 2~6h of Ball-milling Time, drum's speed of rotation 875rap/
Min obtains alloy powder.
9. preparation method according to claim 8, which is characterized in that in step S3, alloyed powder and EG-SnO2In high-purity argon
10~30min of high-energy ball milling in short-term under gas shielded.
10. preparation method according to claim 3, which is characterized in that in step S3, by obtained alloyed powder and EG-SnO2
Ball grinder, EG-SnO are added simultaneously2Account for 0~20wt.%, EG:SnO2=(1~2): (2~1).
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