CN105478019B - A kind of composition metal Hydrogen Separation film and its preparation method and application - Google Patents
A kind of composition metal Hydrogen Separation film and its preparation method and application Download PDFInfo
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- CN105478019B CN105478019B CN201410482668.4A CN201410482668A CN105478019B CN 105478019 B CN105478019 B CN 105478019B CN 201410482668 A CN201410482668 A CN 201410482668A CN 105478019 B CN105478019 B CN 105478019B
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Abstract
The invention discloses a kind of composition metal Hydrogen Separation film and preparation method thereof and the application of the composition metal Hydrogen Separation film in dehydrogenation reaction, which includes porous stainless steel layer and zinc oxide and the composite membrane of palladium metal in the porous stainless steel layer.The composition metal Hydrogen Separation film provided according to the present invention can effectively carry out the separation of hydrogen, improve the yield of the reaction product of dehydrogenation reaction, combination is strong between simultaneous oxidation zinc and palladium metal composite membrane and porous stainless steel, efficiently solves the sintering phenomenon of high-temperature metal palladium film.In addition, the preparation method of composition metal Hydrogen Separation film provided by the invention, operation is simple, beneficial to popularization and application.
Description
Technical field
The present invention relates to a kind of composition metal Hydrogen Separation film and preparation method thereof and the composition metal Hydrogen Separation film to exist
Application in dehydrogenation reaction.
Background technology
Gaseous jet simulation is a kind of green technology, and since it has, separative efficiency is high, energy consumption is low, simple operation and other advantages,
Unique advantage is shown in the competition with conventional separation techniques (absorption, absorption, cryogenic separation etc.), it is studied and application hair
Exhibition is very rapid.
Inoranic membrane can be divided into dense film and perforated membrane by surface structure form.Dense film mainly has each metalloid and its alloy
Film (such as Pd and Pd alloy films), fine and close solid electrolyte film (such as complex solid oxidation film), perforated membrane mainly has porous
Metal film (such as Ti, Ag, Ni, Pd), porous ceramic film (such as Al2O3、SiO2, cellular glass, ZrO2、TiO2Deng), molecular screen membrane (bag
Include Carbon Molecular Sieve Membrane) etc..Compared to dense film, perforated membrane can substantially reduce the cost of film and improve gas permeability.Meanwhile
Since inorganic porous membrane has more preferable high-temperature stability, it is integrated with catalytic reaction membrane catalytic reactor is made, can be with
Two aspect raising catalytic reaction transformation efficiencies and selectivity occurs by improving kinetics, suppressing side reaction.
Wherein, as hydrogen as energy source is increasingly paid attention to and paid close attention to, UF membrane recycling hydrogen has become application at present most
More, most ripe field.Metal Palladium has hydrogen the dissolubility and diffusivity of uniqueness, and making palladium film, (including pure palladium film and palladium close
Golden film) there is considerable hydrogen permeability and selectivity.Wherein U.S. Power Energy companies once illustrated it in 2006
Hydrogen gas segregator based on palladium-based composite membrane, it separates hydrogen ability and reaches 50kW, it can be with the steam reformation such as methane, ethanol, ammonia
It is combined, for the separation of hydrogen, can be also used for the separation of hydrogen during synthesis gas, biological decomposition etc..
The various catalytic reactions in relation to hydrogen can be carried out using palladium film reactor, constantly by the hydrogen in reaction product from anti-
Answer sidesway to walk, so as to improve reaction conversion ratio and reduce reaction temperature etc., reaction and separated one is realized in palladium film reactor
Body.
Common dehydrogenation reaction has preparing propylene by dehydrogenating propane, preparing isobutene through dehydrogenation of iso-butane and ethyl benzene dehydrogenation preparation of styrene
Deng.She Y etc. react palladium film reactor for ethyl benzene dehydrogenation preparation of styrene, and the shifting hydrogen under 625 DEG C of high temperature due to palladium film acts on,
Make selectivity of the styrene in membrane reactor than high in fixed bed, so as to improve styrene yield.Hydrogen production reaction has first
Alkane steam reformation, methanol steam reforming and water gas shift reaction etc..Hydrogenation reaction has catalyzing carbon monoxide preparing methanol by hydrogenation
Palladium-silver membrane reactor is used in traditional carbon monoxide synthesizing methanol second reactor Deng, Rahimpour M R etc., is improved
CO conversion.Preparing phenylethylene from dehydrogenation of phenylethane reaction is catalyzed by Moustafat T M etc. in membrane reactor with benzene
Preparing cyclohexane reaction coupling is hydrogenated with, conversion of ethylbenzene is higher than equilibrium conversion, reaches 87%.Farsi M etc. are in palladium-silver
Making dimethyl ether with methanol catalytic dehydration process is reacted in membrane reactor and is coupled with the reaction of second producing cyclohexane by benzene hydrogenation, Catalytic dehydration of methanol system
Dimethyl ether is exothermic reaction, and second producing cyclohexane by benzene hydrogenation is the endothermic reaction, both optimize integration in membrane reactor, improve heat
Efficiency, reduces reactor volume, and methanol conversion improves 2.76%.
The Hydrogen Separation film used at present uses Woelm Alumina or porous stainless steel as carrier more, using chemical plating
Method prepare Metal Palladium or palladium metal composite membrane.However, there is serious be stranded in porous oxidation aluminum pipe in terms of welding with intensity
Difficulty, and porous stainless steel is since there are spread to influence the service life of film between metal between metal film.Some researchs
Attempt to solve the problems, such as to spread between metal by covering aluminum oxide coating, yet with metal and aluminium oxide ceramics thermal coefficient of expansion
The problem of different and surface wettability so that weak sintering phenomenon for causing high-temperature metal palladium film low with elevated temperature strength of bond strength etc.
Problem.
Therefore, there is an urgent need for develop a kind of anchor cooperation use that can strengthen palladium film and carrier and improve palladium film thermal cycle for this area
The high efficiency hydrogen seperation film of stability.
The content of the invention
It is an object of the invention to overcome in existing Hydrogen Separation film porous stainless steel and metal, intermembranous there are between metal
The defects of diffusion and porous stainless steel and weak metal film bond strength, there is provided a kind of composition metal Hydrogen Separation film and its preparation
Method and the application of the composition metal Hydrogen Separation film in dehydrogenation reaction.
The present inventor has found by studying, by porous stainless steel surface synthesizing zinc oxide film, then again with
This is templated synthesis zinc oxide and the composite membrane of palladium metal, and obtained composite metal membrane, can efficiently solve porous stainless
Steel and metal are intermembranous there are diffusion problem between metal, and porous stainless steel is combined with metal film in gained composition metal composite membrane
Intensity is high, can effectively solve the problem that the problem of high-temperature metal film sinters.
To achieve these goals, in a first aspect, the present invention provides a kind of composition metal Hydrogen Separation film, the seperation film bag
Include porous stainless steel layer and zinc oxide and the composite membrane of palladium metal in the porous stainless steel layer.
Second aspect, the present invention also provides a kind of preparation method of above-mentioned composition metal Hydrogen Separation film, this method includes
Following steps：
(1) porous stainless steel is immersed in the mixed solution containing water-soluble zinc salt and hexa and carries out the first water
Thermal response, obtains being attached with the porous stainless steel of zinc oxide；
(2) porous stainless steel for being attached with zinc oxide for obtaining step (1) immerse in the aqueous solution of water-soluble palladium salt into
The second hydro-thermal reaction of row.
The third aspect, prepares compound the present invention also provides a kind of preparation method by above-mentioned composition metal hydrogen composite membrane
Metal hydrogen composite membrane.
Fourth aspect, the present invention also provides a kind of application of above-mentioned composition metal hydrogen composite membrane in dehydrogenation reaction.
The composition metal Hydrogen Separation film provided according to the present invention, can overcome porous stainless steel intermembranous in the presence of gold with metal
Diffusion problem between category so that the film has longer service life, meanwhile, porous stainless steel and metal film bond strength in the film
It is high so that the film has more preferable thermal cycling stability, can effectively solve the problem that the problem of high-temperature metal film sinters.
Can effectively it be improved instead in addition, the composition metal Hydrogen Separation film provided according to the present invention is applied to dehydrogenation reaction
Answer the yield of product.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the SEM figures on the porous stainless steel used in the embodiment of the present invention 1 surface after pretreatment.
Fig. 2 is the SEM figures of the porous stainless steel used in the embodiment of the present invention 1 cross section after pretreatment.
Fig. 3 is the SEM figures for the nanometic zinc oxide rod array being attached in the embodiment of the present invention 1 on porous stainless steel.
Fig. 4 is that the SEM of the zinc oxide and palladium metal composite membrane in the embodiment of the present invention 1 schemes.
Fig. 5 is that the SEM of the zinc oxide and palladium metal composite membrane in the comparative example 1 of the present invention schemes.
Fig. 6 is the reactor that device has Hydrogen Separation membrane tube.
Fig. 7 be composition metal Hydrogen Separation film in the embodiment of the present invention 1 at various pressures hydrogen infiltration capacity with temperature
The variation tendency of degree.
Fig. 8 be composition metal Hydrogen Separation film in the embodiment of the present invention 1 at various pressures hydrogen infiltration capacity with temperature
The variation tendency of degree.
Fig. 9 be composition metal Hydrogen Separation film in the embodiment of the present invention 1 at various pressures hydrogen infiltration capacity with temperature
The variation tendency of degree.
Figure 10 is the Hydrogen Separation film hydrogen infiltration capacity variation with temperature at various pressures in the comparative example 1 of the present invention
Trend.
Figure 11 is the Hydrogen Separation film hydrogen infiltration capacity variation with temperature at various pressures in the comparative example 1 of the present invention
Trend.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of composition metal Hydrogen Separation film, which includes porous stainless steel layer and more at this
The composite membrane of zinc oxide and palladium metal on the stainless steel layer of hole.
Composition metal Hydrogen Separation film provided by the invention, can be widely applied for the separation of hydrogen, especially suitable for dehydrogenation
The separation of hydrogen in reaction process.
The present inventor further study show that, zinc oxide presence in the form of nanometer stick array can improve
Be combineding with each other between metallic zinc and palladium, so that the thermal cycling stability of the composition metal Hydrogen Separation film is further improved,
In the case of it is therefore preferable that, in the composite membrane, the zinc oxide exists in the form of nanometer stick array.
In the case of in the present invention, it is preferred to, in the composite membrane, the weight ratio of zinc oxide and palladium metal is 0.02-10：
1, more preferably 1-8：1.
In the case of in the present invention, it is preferred to, the average film thickness of the composite membrane is 5-10 microns.
In the present invention, be not particularly limited for the porous stainless steel layer, under preferable case, it is described it is porous not
The average pore diameter for steel layer of becoming rusty is 0.5-1.2 microns, and thickness is 0.5-1.5 millimeters, porosity 20-40%.Further preferably
In the case of, the average pore diameter of the average hole porous stainless steel of the porous stainless steel layer is 0.8-1.1 microns, thickness 0.7-
1.2 millimeters, porosity 25-35%.
In the present invention, for the shape of the porous stainless steel layer, there is no particular limitation, described more under preferable case
Hole stainless steel layer is porous stainless steel, and the porous stainless steel can be commercially available, such as 316L porous stainless steels.
It is not particularly limited for the outside diameter of the porous stainless steel, such as can is 1-6 microns.
Present invention also offers a kind of preparation method of composition metal Hydrogen Separation film, this method comprises the following steps：
(1) porous stainless steel is immersed in the mixed solution containing water-soluble zinc salt and hexa and carries out the first water
Thermal response, obtains being attached with the porous stainless steel of zinc oxide；
(2) porous stainless steel for being attached with zinc oxide for obtaining step (1) immerse in the aqueous solution of water-soluble palladium salt into
The second hydro-thermal reaction of row.
In the case of in the present invention, it is preferred to, in the mixed solution, the molar concentration of the water-soluble zinc salt is
0.01-0.2mol/L, the molar concentration of the hexa is 0.01-0.2mol/L.
In the present invention, be not particularly limited for the weight of the mixed solution, as long as so that it is described it is porous not
Rust steel, which can be immersed into the mixed solution, sufficiently to be contacted.
In the aqueous solution of the water-soluble palladium salt, under preferable case, the molar concentration of the water solubility palladium salt is 0.01-
0.05mol/L。
In the present invention, for the water-soluble zinc salt, hexa and the not special limit of water-soluble palladium salt
It is fixed, can be water-soluble zinc salt commonly used in the art, such as the water-soluble zinc salt can be zinc nitrate, zinc acetate, sulphur
One or more in sour zinc and zinc chloride, are preferably zinc nitrate；The water solubility palladium salt can be palladium nitrate, PdCl2、Pd
(NH3)2(NO3)2、Pd(NH3)2Cl2、Pd(NH3)2Br2、Pd(NH3)4Cl2With Pd (NH3)4Br2In one or more, be preferably
Palladium nitrate.
In the case of in the present invention, it is preferred to, in step (1), the condition of first hydro-thermal reaction includes：The temperature of reaction
Spend for 85-120 DEG C, the time of reaction is 2-24h.
In the case of in the present invention, it is preferred to, in step (2), the condition of second hydro-thermal reaction includes：The temperature of reaction
Spend for 60-120 DEG C, the time of reaction is 0.5-4h.
In the case of in the present invention, it is preferred to, the average pore diameter of the porous stainless steel is 0.5-1.2 microns, and thickness is
0.5-1.5 millimeters, porosity 20-40%.In the case of further preferably, the average hole porous stainless steel of the porous stainless steel
Average pore diameter be 0.8-1.1 micron, thickness be 0.7-1.2 millimeters, porosity 25-35%.For the porous stainless
There is no particular limitation for the shape of steel, such as can be porous stainless steel, and the porous stainless steel can be obtained by commercially available
, such as 316L porous stainless steels.It is not particularly limited for the outside diameter of the porous stainless steel, such as can is 1-
6 microns.
It is described before the porous stainless steel immerses mixed solution in step (1) in the case of in the present invention, it is preferred to
Porous stainless steel will be pre-processed, and be not particularly limited for the method for the pretreatment, such as the porous stainless
The method that steel is pre-processed can be：Successively with 5% sodium hydroxide solution, the dilute nitric acid solution or concentrated hydrochloric acid of 10-40%
The porous stainless steel is cleaned, is then washed with deionized water to neutrality, finally with washes of absolute alcohol and in 60-120
Dried at DEG C.
Present invention also offers the composition metal hydrogen of the preparation method preparation by above method composition metal Hydrogen Separation film
Gas seperation film.
In addition, the application present invention also offers above-mentioned composition metal Hydrogen Separation film in dehydrogenation reaction.
In the present invention, the method for the application for composition metal Hydrogen Separation film in dehydrogenation reaction is not special
Limit, such as the composition metal Hydrogen Separation film of gained can be fixedly mounted in the reactor of dehydrogenation reaction (as shown in Figure 6
Device have the reactor of Hydrogen Separation film), then carry out the separation that dehydrogenation reaction carries out hydrogen.The dehydrogenation reaction is ability
Well known to field technique personnel, such as can be ammonia decomposition reaction, dehydrogenating propane reaction etc..
The present invention will be described in detail by way of examples below.
In following embodiments and comparative example, the 316L porous stainless steels of various specifications are Xibei Inst. of Non-Ferrous Metals
Commercially available product.
Embodiment 1
In the present invention, porous stainless steel be average pore diameter be 1 micron, thickness is 0.5 millimeter, porosity is 30% and
Outside diameter is 1 millimeter of 316L porous stainless steels.
The pretreatment of porous stainless steel：Successively with 5% sodium hydroxide solution, 40% dilute nitric acid solution to described more
Hole stainless steel tube is cleaned, and is then washed with deionized water to neutrality, is finally dried with washes of absolute alcohol and at 100 DEG C.
The preparation of composition metal Hydrogen Separation film：
(1) the above-mentioned porous stainless steel handled well is immersed sub- containing water-soluble zinc salt (zinc nitrate 0.1mol/L) and six
The first hydro-thermal reaction is carried out in the mixed solution of tetramine (0.1mol/L), obtains being attached with the porous stainless steel of zinc oxide
Pipe, the condition of first hydro-thermal reaction include：The temperature of reaction is 95 DEG C, when the time of reaction is 4 small；
(2) porous stainless steel for being attached with zinc oxide for obtaining step (1) is immersed in the aqueous solution of water-soluble palladium salt
(palladium nitrate, 0.01mol/L) carries out the second hydro-thermal reaction, and the condition of second hydro-thermal reaction includes：The temperature of reaction is 95
DEG C, when the time of reaction is 2 small, composition metal Hydrogen Separation film A1 is obtained, wherein, the composite membrane of zinc oxide and palladium metal is averaged
Thickness is 5-10 microns, and in the composite membrane, the weight ratio of zinc oxide and palladium metal is 1：1.
Embodiment 2
In the present invention, porous stainless steel be average pore diameter be 1.2 microns, thickness is 1 millimeter, porosity is 40% and
Outside diameter is 4 millimeters of 316L porous stainless steels.
The pretreatment of porous stainless steel：Successively with 5% sodium hydroxide solution, 30% dilute nitric acid solution to described more
Hole stainless steel tube is cleaned, and is then washed with deionized water to neutrality, is finally dried with washes of absolute alcohol and at 120 DEG C.
The preparation of composition metal Hydrogen Separation film：
(1) the above-mentioned porous stainless steel handled well is immersed sub- containing water-soluble zinc salt (zinc nitrate 0.1mol/L) and six
The first hydro-thermal reaction is carried out in the mixed solution of tetramine (0.1mol/L), obtains being attached with the porous stainless steel of zinc oxide
Pipe, the condition of first hydro-thermal reaction include：The temperature of reaction is 85 DEG C, when the time of reaction is 24 small；
(2) (nitre in the aqueous solution for the water-soluble palladium salt of the porous stainless steel for being attached with zinc oxide immersion for obtaining step (1)
Sour palladium, 0.05mol/L) the second hydro-thermal reaction is carried out, the condition of second hydro-thermal reaction includes：The temperature of reaction is 120 DEG C,
When the time of reaction is 0.5 small, composition metal Hydrogen Separation film A2 is obtained, wherein, the composite membrane of zinc oxide and palladium metal is averaged
Thickness is 5-10 microns, and in the composite membrane, the weight ratio of zinc oxide and palladium metal is 8：1.
Embodiment 3
In the present invention, porous stainless steel be average pore diameter be 0.5 micron, thickness is 1.5 millimeters, porosity 20%
With the 316L porous stainless steels that outside diameter is 6 millimeters.
The pretreatment of porous stainless steel：Successively with 5% sodium hydroxide solution, concentrated hydrochloric acid to the porous stainless steel
Cleaned, be then washed with deionized water to neutrality, finally dried with washes of absolute alcohol and at 80 DEG C.
The preparation of composition metal Hydrogen Separation film：
(1) the above-mentioned porous stainless steel handled well is immersed sub- containing water-soluble zinc salt (zinc nitrate 0.1mol/L) and six
The first hydro-thermal reaction is carried out in the mixed solution of tetramine (0.1mol/L), obtains being attached with the porous stainless steel of zinc oxide
Pipe, the condition of first hydro-thermal reaction include：The temperature of reaction is 120 DEG C, when the time of reaction is 2 small；
(2) (nitre in the aqueous solution for the water-soluble palladium salt of the porous stainless steel for being attached with zinc oxide immersion for obtaining step (1)
Sour palladium, 0.03mol/L) the second hydro-thermal reaction is carried out, the condition of second hydro-thermal reaction includes：The temperature of reaction is 60 DEG C,
When the time of reaction is 4 small, composition metal Hydrogen Separation film A3 is obtained, wherein, the average thickness of composite membrane of zinc oxide and palladium metal
Spend for 5-10 microns, in the composite membrane, the weight ratio of zinc oxide and palladium metal is 4：1.
Comparative example 1
Using porous stainless steel same as Example 1 and pre-processed.
The coating alumina on porous stainless steel：(1) deionized water is added in round-bottomed flask, added to 85 DEG C,
It is vigorously stirred down, adds aluminium isopropoxide, hydrolysis 30min obtains milk-white coloured suspension, is obtained when then adding nitric acid and small time sulphur 12
To alumina sol, the addition molar ratio of the deionized water, aluminium isopropoxide and nitric acid is 300：1：0.22；(2) vacuum is used
Absorption method is by alumina sol coated on porous stainless steel；(3) under air and nitrogen atmosphere 500 DEG C respectively annealing it is 4 small
When, wherein, gas flow 20ml/min.
The preparation of Hydrogen Separation film：Porous stainless steel obtained above coated with aluminium oxide is immersed into water-soluble palladium salt
(palladium nitrate, 0.1mol/L) carries out the second hydro-thermal reaction in aqueous solution, and the condition of second hydro-thermal reaction includes：The temperature of reaction
Spend for 95 DEG C, when the time of reaction is 2 small, obtain Hydrogen Separation film D1.
Comparative example 2
Using porous stainless steel same as Example 1 and pre-processed.
The preparation of Hydrogen Separation film：Pretreated porous stainless steel is directly immersed in the aqueous solution of water-soluble palladium salt
(palladium nitrate, 0.01mol/L) carries out hydro-thermal reaction, and the condition of hydro-thermal reaction includes：The temperature of reaction is 95 DEG C, the time of reaction
For 2 it is small when, obtain Hydrogen Separation film D2.
Test case 1-3 and contrast test 1-2
The Hydrogen Separation film that composition metal Hydrogen Separation film A1-A3 and comparative example 1-2 that embodiment 1-3 is obtained are obtained
D1-D2 carries out hydrogen permeability test.Experimental result is as illustrated in figures 7-11.
Hydrogen permeability is tested：Hydrogen permeability test has in device as shown in Figure 6 to be carried out on the reactor of Hydrogen Separation membrane tube, right
Hydrogen Separation membrane tube is tested respectively when being composition metal Hydrogen Separation film A1-A3 and Hydrogen Separation film D1-D2.Test process
For：With High Purity Nitrogen by the gas displacement 5 times of inlet plenum, lead to nitrogen 30min, then heat to 300 DEG C, with hydrogen by feed side gas
Indoor nitrogen displacement, permeability test is carried out under the conditions of pressure is 0.1-0.14MPa and temperature is 300-500 DEG C.
Can be seen that composition metal Hydrogen Separation film A1-A3 provided by the invention from Fig. 7-Figure 11 all has good hydrogen
Gas permeability, hydrogen permeability can increase with pressure and increase and with good stability, and although D2 have it is good
Hydrogen permeability, but simultaneously Hydrogen Brittleness Phenomena occurs for the progress that D2 increases and tests with pressure, its bad stability.
Application examples 1
Device as shown in Figure 6 has the reactor of Hydrogen Separation membrane tube, wherein, Hydrogen Separation membrane tube is the gained of embodiment 1
Composition metal Hydrogen Separation film.Using the gaseous mixture of propane (20mol%) and nitrogen as unstripped gas, gas flow 30ml/
min.Argon gas is purge gas, will constantly be removed by the gas of composition metal Hydrogen Separation film, gas flow 100ml/
min.The reaction temperature of dehydrogenating propane is 500 DEG C, and when the reaction time is 48 small, the yield for measuring propylene is 50%.
Application examples 2-3 and contrast application examples 1-2
According to the method for Application Example 1, the difference is that Hydrogen Separation membrane tube is respectively answering obtained by embodiment 2-3
Hydrogen Separation film D1, D2 obtained by alloy category Hydrogen Separation film A2, A3 and comparative example 1-2, the yield for measuring propylene are respectively
40%th, 42%, 35% and 30%.
Composition metal hydrogen provided by the invention is can be seen that from the yield of propylene obtained by application examples 1-3 and contrast application examples
Gas seperation film can effectively improve the yield of propylene in dehydrogenation reaction.
In conclusion the composition metal Hydrogen Separation film provided according to the present invention can effectively carry out the separation of hydrogen,
So as to promote the progress of dehydrogenation reaction, the yield of reaction product, simultaneous oxidation zinc and palladium metal composite membrane and porous stainless are improved
Combination is strong between steel, efficiently solves the sintering phenomenon of high-temperature metal palladium film.
In addition, the preparation method of composition metal Hydrogen Separation film provided by the invention, operation is simple, should beneficial to promoting
With.
Claims (15)
1. a kind of composition metal Hydrogen Separation film, which includes porous stainless steel layer and in the porous stainless steel layer
The composite membrane of zinc oxide and palladium metal, in the composite membrane, the zinc oxide exists in the form of nanometer stick array.
2. seperation film according to claim 1, wherein, in the composite membrane, the weight ratio of zinc oxide and palladium metal is
0.02-10：1.
3. seperation film according to claim 2, wherein, in the composite membrane, the weight ratio of zinc oxide and palladium metal is
1-8：1.
4. according to the seperation film described in any one in claim 1-3, wherein, the average film thickness of the composite membrane is micro- for 5-10
Rice.
5. seperation film according to claim 1, wherein, the average pore diameter of the porous stainless steel layer is micro- for 0.5-1.2
Rice, thickness are 0.5-1.5 millimeters, porosity 20-40%.
6. seperation film according to claim 5, wherein, the average pore diameter of the porous stainless steel layer is micro- for 0.8-1.1
Rice, thickness are 0.7-1.2 millimeters, porosity 25-35%.
7. a kind of preparation method of the composition metal Hydrogen Separation film in claim 1-6 described in any one, this method include
Following steps：
(1) porous stainless steel is immersed in the mixed solution containing water-soluble zinc salt and hexa that to carry out the first hydro-thermal anti-
Answer, obtain being attached with the porous stainless steel of zinc oxide；
(2) the obtained porous stainless steel for being attached with zinc oxide of step (1) is immersed in the aqueous solution of water-soluble palladium salt and carries out the
Two hydro-thermal reactions.
8. according to the method described in claim 7, wherein, in the mixed solution, the molar concentration of the water-soluble zinc salt
For 0.01-0.2mol/L, the molar concentration of the hexa is 0.01-0.2mol/L；
In the aqueous solution of the water-soluble palladium salt, the molar concentration of the water solubility palladium salt is 0.01-0.05mol/L.
9. the method according to claim 7 or 8, wherein, the water-soluble zinc salt is zinc nitrate, zinc acetate, zinc sulfate and
One or more in zinc chloride；The water solubility palladium salt is palladium nitrate, PdCl2、Pd(NH3)2(NO3)2、Pd(NH3)2Cl2、Pd
(NH3)2Br2、Pd(NH3)4Cl2With Pd (NH3)4Br2In one or more.
10. according to the method described in claim 9, wherein, the water-soluble zinc salt is zinc nitrate.
11. according to the method described in claim 9, wherein, the water solubility palladium salt is palladium nitrate.
12. according to the method described in claim 7, wherein, in step (1), the condition of first hydro-thermal reaction includes：Instead
The temperature answered is 85-120 DEG C, and the time of reaction is 2-24h.
13. according to the method described in claim 7, wherein, in step (2), the condition of second hydro-thermal reaction includes：Instead
The temperature answered is 60-120 DEG C, and the time of reaction is 0.5-4h.
14. the preparation method of the composition metal Hydrogen Separation film according to any one in claim 7-13 is prepared compound
Metal Hydrogen Separation film.
15. application of the composition metal Hydrogen Separation film in dehydrogenation reaction in claim 1-6 and 14 described in any one.
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| US9682346B1 (en) * | 2016-10-20 | 2017-06-20 | Sultan Qaboos University | Nanostructured zinc oxide membrane for separating oil from water |
| CN109574782A (en) * | 2019-01-24 | 2019-04-05 | 内江师范学院 | A kind of reaction unit and technique in the source C1 and alkylation of toluene production styrene |
| CN110548482A (en) * | 2019-09-26 | 2019-12-10 | 中国原子能科学研究院 | preparation method of stainless steel-based molecular sieve membrane material for adsorbing uranium hexafluoride |
| CN112176285A (en) * | 2020-09-24 | 2021-01-05 | 李新中 | Novel niobium carbide film for hydrogen separation and preparation method thereof |
| CN113560708B (en) * | 2021-07-29 | 2022-06-28 | 西安天力金属复合材料股份有限公司 | Method for connecting palladium-based alloy film and porous stainless steel carrier |
| CN116651219B (en) * | 2023-06-06 | 2024-02-09 | 广东省科学院中乌焊接研究所 | Palladium-copper-zinc alloy film for hydrogen separation and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN101219804A (en) * | 2008-01-22 | 2008-07-16 | 北京科技大学 | Method for producing soakage controllable zinc oxide nano-stick array thin film |
| CN102024955A (en) * | 2010-10-30 | 2011-04-20 | 湖南科技大学 | Three-dimensional mesh nano porous palladium-ruthenium electrode material for fuel cell and preparation method thereof |
| JP4714052B2 (en) * | 2006-03-16 | 2011-06-29 | 大日本印刷株式会社 | Hydrogen purification filter and method for producing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4714052B2 (en) * | 2006-03-16 | 2011-06-29 | 大日本印刷株式会社 | Hydrogen purification filter and method for producing the same |
| CN101219804A (en) * | 2008-01-22 | 2008-07-16 | 北京科技大学 | Method for producing soakage controllable zinc oxide nano-stick array thin film |
| CN102024955A (en) * | 2010-10-30 | 2011-04-20 | 湖南科技大学 | Three-dimensional mesh nano porous palladium-ruthenium electrode material for fuel cell and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Hydrogen generation in a Pd membrane fuel processor: assessment of methanol-based reaction systems;Michael P.Harold等;《Chemical Engineering Science》;20030630;第58卷(第12期);全文 * |
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