CN105013339A - Method for preparing molecular sieve membrane on surface of metal palladium membrane - Google Patents
Method for preparing molecular sieve membrane on surface of metal palladium membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing molecular sieve membrane on the surface of a metal palladium membrane. According to the invention, in-situ synthesis is carried out on the surface of the palladium membrane with a multipore ceramic serving as a substrate to synthesize a molecular sieve membrane so as to prepare a composite membrane with a bottom membrane-palladium membrane-molecular sieve membrane three-layer structure. The three-layer structures of the composite membrane are tightly combined, so that a sandwich structure with the palladium membrane serving as the middle layer is formed. The structure can suppress breakage damage caused by deformation of the palladium membrane, so that the property against hydrogen embrittlement of the palladium membrane under a low-temperature condition is improved, and the service life of the palladium membrane is prolonged. Meanwhile, by the sieving performance of the sieve membrane to molecules, contact between impurity gas and the palladium membrane can be prevented, and the toxic effect of the impurity gas on the palladium membrane can be suppressed. According to the method, hydrogen embrittlement resistance and poisoning resistance protection measures are provided for a palladium-based hydrogen separation membrane, so that use range of the palladium membrane is expanded, and the service life of the palladium membrane is prolonged; the palladium membrane can be widely applied.
Description
Technical field
The present invention relates to the method that molecular screen membrane is prepared on a kind of Metal Palladium film surface, this preparation method is growth in situ porous molecular sieve membrane on the metal film of densification, the separating-purifying of (less than 300 DEG C) hydrogen under this composite membrane can be used for cryogenic conditions, also can be used for the separating-purifying containing the hydrogen of poisoning foreign gas, in palladium film Selective Separation hydrogen process, expand the serviceability temperature of palladium film and improve the stability of palladium film, the anti-hydrogen embrittlement of main enhancing palladium film, anti-foreign gas are poisoned and are corroded and mechanical wear resistance energy, belong to technical field of membrane separation.
Background technology
Hydrogen Energy occupies very important status in the energy resource system in future.Along with developing rapidly of Hydrogen Energy, it is produced accordingly, be separated, the research of accumulating and application links also obtains the attention in many fields such as the energy, chemical industry.Hydrogen is separated an important step as Hydrogen Energy system, and its development also plays very important effect to Hydrogen Energy system.
Along with the difference of hydrogen purposes, there is different requirements to its purity.Numerous national substantial industrial productions such as semiconductor, electronics industry, production of polysilicon, LED manufacture all be unable to do without the ultra-pure hydrogen that purity is greater than 99.9999%.The isolation and purification technology of hydrogen in plant-scale hydrogen-containing gas, mainly cold separation technology, pressure-variable adsorption PSA technology and organic film gas separation.But by the restriction of the principle of technology own, these technology separation hydrogen purities are limited, be the highlyest no more than 99.999%, the industry with high-purity demand can not be met.At present, the production of the ultra-pure hydrogen of industrial purity more than 99.9999% realizes mainly through metal palladium tube.But, the thickness of metal palladium tube generally tens to micron up to a hundred, consume a large amount of precious metal palladium, expensive.Its ultra-pure hydrogen yields poorly, and maintenance cycle is long, and easy hydrogen embrittlement damages, and is difficult to the extensive use meeting futurity industry production.Therefore, be deposited on porous supporting body by Metal Palladium or palldium alloy, make the palladium film or palladium alloy membrane that only have several micron thickness, replacing Metal Palladium control to get ultra-pure hydrogen is following development trend.Compared with palladium tube, the permeated hydrogen amount of metal palladium-based composite membrane significantly improves, and cost significantly reduces, and have very important using value for cheapness production, efficient separation and purification hydrogen, future has broad application prospects.
Present stage, be exactly that palladium film can cause crack damage because of hydrogen embrittlement problem under cryogenic (less than 300 DEG C) by a common problem of Metal Palladium purifying hydrogen of hydrogen technology, cause palladium film to lose the selective ability through hydrogen completely.Hydrogen Brittleness Phenomena refers in presence of hydrogen, and pure palladium film, below 300 DEG C, α → β phase transformation can occur, and the change of lattice parameter brings mechanical stress to fine and close palladium film inside, and the release of stress can make palladium film that larger mechanical deformation occurs.Bending and the embrittlement of this membrane material can cause local, palladium film surface to occur larger breakdown point, causes the irreversible damage of palladium film.Experiment proves, at low temperatures, palladium film is very responsive to hydrogen, even if the hydrogen be adsorbed on a small quantity on palladium film or reactor all can cause irreversible infringement to palladium film.This makes the serviceability temperature of palladium film must be strict controlled in more than 300 DEG C, and parking of can not lowering the temperature when not using.Therefore, hydrogen embrittlement problem significantly limit the range of application of palladium film purifying hydrogen of hydrogen technology, and in commercial Application, there is great destabilizing factor, as having a power failure suddenly, the situation such as firing equipment damages suddenly, start-stop car, the equal palladium film that can make contacts hydrogen at a lower temperature, cause the damage of palladium film, affect the service life of palladium film.At present, by the metals such as palladium and silver, copper, gold and ruthenium are formed alloy, phase transition temperature can be made to extend to low temperature, widen the serviceability temperature of palladium film, reduce the danger of hydrogen embrittlement.But, the complexity prepared of palladium alloy membrane and uncertain, alloying process energy consumption is large and the time is long etc., and problem does not also well solve, industrialization can't be met and use on a large scale.Except use palladium alloy membrane, domestic and international research institution does not all have good solution to this problem of hydrogen embrittlement.Hydrogen embrittlement problem seriously constrains the application of metal palladium-based composite membrane, brings difficulty and destabilizing factor to the commercial Application of palladium film.
Molecular sieve is the crystalline microporous material with regular duct, and its duct is interconnected by atoms such as silicon, aluminium, oxygen to form.Molecular screen membrane is the unlimited extension that in molecular screen material, each atom is interconnected growth, has mechanical strength height and is connected feature closely with film internal structure.Molecular screen membrane, in the growth of palladium film surface in situ, is all combined with palladium film close everywhere, and palladium film owing to being subject to the restriction of molecular screen membrane, larger mechanical deformation can not occur undergoing phase transition in process, thus protects palladium film that hydrogen embrittlement damage does not occur.
The present invention is directed to the problem that hydrogen embrittlement easily occurs at low temperature metal palladium-based composite membrane, propose a kind of method that Metal Palladium film surface in situ prepares molecular screen membrane, prepare one with Metal Palladium film for intermediate layer, surface is molecular screen membrane, and bottom is the sandwich structure composite membrane of porous supporting body layer.Different with the principle of traditional anti-hydrogen embrittlement ability by raising Metal Palladium film itself, anti-hydrogen embrittlement principle of the present invention utilizes the strong interaction of molecular screen membrane and Metal Palladium film and the higher mechanical strength of molecular screen membrane itself, suppress Metal Palladium film that larger mechanical deformation occurs in phase transition process, thus improve the anti-hydrogen embrittlement performance of Metal Palladium film, extend the service life of palladium film.In addition, because prepared molecular screen membrane duct is less, molecule is had to the effect of screening, therefore, this molecular screen membrane can hinder foreign gas to contact with palladium film, prevents palladium film by the toxic action of foreign gas, carries out available protecting to palladium film.
Summary of the invention
The object of the invention is to solve the problem that hydrogen embrittlement and breakage easily occur palladium film at low temperatures, widen range of application and the service life of palladium UF membrane hydrogen, a kind of method protecting palladium film is provided.
For achieving the above object, the present invention proposes following technical scheme: at palladium membrane surface growth in situ molecular screen membrane, utilize the strong interaction of molecular screen membrane and Metal Palladium film and the higher mechanical strength of molecular screen membrane itself, suppress Metal Palladium film that larger mechanical deformation occurs in phase transition process, thus improve the anti-hydrogen embrittlement performance of Metal Palladium film, extend the service life of palladium film.
Preparation method of the present invention first prepares palladium film on counterdie, then on palladium film, prepares molecular screen membrane.When preparing molecular screen membrane, do not need seeded and add other connecting medias, directly at Metal Palladium film surface in situ growth molecular screen membrane, palladium film and molecular screen membrane being combined closely.
The method of the composite membrane of the counterdie prepared by the present invention-palladium film-molecular screen membrane three-decker is as follows: (1) prepares palladium film on porous counterdie; (2) palladium film diluted acid is carried out surface treatment; (3) the palladium film after process is placed in the reactor that Zeolite synthesis liquid is housed; (4) at 80-150 DEG C, synthesize 1-15 hour, the superficial growth of palladium film goes out molecular screen membrane; (5) composite membrane of counterdie-palladium film-molecular screen membrane three-decker is obtained after molecular screen membrane being washed till neutrality.
Palladium film diluted acid is carried out surface treatment, can be adopted any one in watery hydrochloric acid, dust technology.The pH value of diluted acid controls between 5.5-6.8, and optimal pH is 6.3.Dilute acid pretreatment time controling is at 5-60 minute, and the optimization process time is 15 minutes.The molecular sieve precursor solution used at palladium film surface synthesizing molecular sieve film is mixed by aluminum feedstock, silicon raw material and alkali, aluminum feedstock is the one in metallic aluminium, sodium metaaluminate, sodium aluminate, aluminum sulfate, silicon raw material is Ludox or sodium metasilicate, alkali is NaOH or potassium hydroxide, is: SiO with the mol ratio of oxide basis
2/ Al
2o
3=2-100, H
2o/Al
2o
3=100-2000, Na
2o/Al
2o
3=2-100, optimizing mol ratio is: SiO
2/ Al
2o
3=2-10, H
2o/Al
2o
3=200-1000, Na
2o/Al
2o
3=10-60.Zeolite synthesis condition is synthesis temperature 80-150 DEG C, and generated time is 1-15 hour, and synthesis number of times is 1-5 time.
In the present invention, in three-decker composite membrane, counterdie is porous supporting body, can be any one in porous ceramics, porous metals, cellular glass; Palladium film is pure palladium film or palladium alloy membrane (molar content of palladium is 20-100%), alloy film can be palladium-silver, palladium copper, porpezite, palladium-nickel alloy film any one; Molecular screen membrane is the porous material that sial base has molecule screening function, comprise zeolite molecular sieve film and Carbon Molecular Sieve Membrane, molecular screen membrane can be any one in the molecular sieve of LTA type (comprising 3A, 4A, 5A type molecular sieve), FAU type (comprising X, Y zeolite), MFI type.Porous counterdie is prepared palladium film, can adopt any one in chemical plating, chemical vapour deposition technique, physical vaporous deposition, galvanoplastic, sputtering method, thickness is 2-20 μm, and the method optimizing palladium plated film is chemical plating, and optimization thickness is 7-9 μm.Molecular screen membrane can adopt hydro-thermal method or microwave method.
During the composite membrane separating hydrogen gas of counterdie in the present invention-palladium film-molecular screen membrane three-decker, hydrogen be from molecular screen membrane side through palladium film thoroughly to counterdie side.The service condition of this composite membrane is 80-500 DEG C, and pressure is 0.1-10MPa.When this composite membrane carries out Hydrogen Separation from gaseous mixture, in gaseous mixture, hydrogen molar concentration is 50-99.99%; In gaseous mixture, remaining gas is one or two or more kinds in nitrogen, carbon monoxide, carbon dioxide, methane, the alkane of C2-C7 or alkene.
In the present invention, the composite membrane low temperature anti-hydrogen embrittlement of three-decker refers under the same conditions, and the composite membrane generation hydrogen embrittlement of counterdie-palladium film double-layer structure damages, and hydrogen embrittlement damage does not occur the composite membrane of counterdie-palladium film-molecular screen membrane three-decker.But composite membrane can undergo phase transition equally under the condition meeting phase transformation, just due to the effect of molecular screen membrane, the stress that this phase transformation produces can not cause breaking of palladium film, namely Hydrogen Brittleness Phenomena can not occur and cause palladium film to lose the ability of Selective Separation hydrogen.As in heating and cooling and buck cyclic process in 150-300 DEG C, 0.1-0.8MPa interval, the composite membrane of the counterdie-palladium film-molecular screen membrane three-decker of purifying for Hydrogen Separation has the stability of low temperature anti-hydrogen embrittlement.
The present invention compared with prior art tool has the following advantages:
1. when preparing molecular screen membrane, do not need seeded and add other connecting medias, directly at Metal Palladium film surface in situ growth molecular screen membrane, molecular screen membrane prepared by the method can grow along with palladium environmental microbes, is combined closely with palladium film.It is incomparable that this technology is that traditional diaphragm prepared taking the lead in covers the technology on palladium film surface;
2. with traditional by preparing palladium alloy membrane etc., to improve the principle of the anti-hydrogen embrittlement ability of Metal Palladium films itself different, anti-hydrogen embrittlement principle of the present invention utilizes the strong interaction of molecular screen membrane and Metal Palladium film and the higher mechanical strength of molecular screen membrane itself, suppress Metal Palladium film that larger mechanical deformation occurs in phase transition process, thus improve the anti-hydrogen embrittlement performance of Metal Palladium film, extend the service life of palladium film;
3. the molecular screen membrane on palladium film surface can completely cut off the murder by poisoning of noxious material to palladium film, also can keep out micronic dust, catalyst granules etc. to the wearing and tearing of palladium film, corrosion, thus protection palladium film, this is that prior art cannot be compared;
4. the molecular screen membrane on palladium film can also be used as the carrier of catalyst or catalyst, and for the integrated form palladium film reactor of catalysis and isolation integral, this is that prior art cannot realize.
Accompanying drawing explanation
Fig. 1 is counterdie-palladium film-molecular screen membrane three-decker composite membrane and anti-hydrogen embrittlement and antitoxin harmful principle schematic;
Fig. 2 is the surface topography map of palladium film superficial growth molecular screen membrane;
Fig. 3 is the Cross Section Morphology figure of palladium film superficial growth molecular screen membrane;
Fig. 4 is the surface topography map of palladium film superficial growth molecular screen membrane in embodiment 1;
Fig. 5 is the surface topography map of palladium film superficial growth molecular screen membrane in embodiment 2;
Fig. 6 is the surface topography map of palladium film superficial growth molecular screen membrane in embodiment 3;
Fig. 7 is the surface topography map of palladium copper film superficial growth molecular screen membrane in embodiment 4;
Fig. 8 is the effect diagram of propylene to the permeated hydrogen amount of different palladium film.
Detailed description of the invention
Counterdie of the present invention-palladium film-molecular screen membrane three-decker composite membrane and anti-hydrogen embrittlement and antitoxin harmful principle schematic are shown in Fig. 1, and the electromicroscopic photograph that prepared palladium membrane surface covers molecular screen membrane is shown in Fig. 2, and its cross section electromicroscopic photograph is shown in Fig. 3.Below in conjunction with detailed description of the invention, the invention will be further described, and protection scope of the present invention is not restricted by the following examples.In embodiment, the preparation process of palladium-based composite membrane is see patent " a kind of composition metal palladium film or alloy palladium film and preparation method thereof ", application number 200410021025.
Method for testing and analyzing used in the present invention:
One, SEM (SEM) is adopted to determine pattern and the thickness of molecular screen membrane.
Two, the anti-hydrogen embrittlement performance of the method test three-decker composite membrane of heating and cooling and lifting pressure circulation is adopted
Three, by detecting this three-decker composite membrane at 5% propylene/H
2the change of the permeated hydrogen amount under gaseous mixture atmosphere, test molecule sieve membrane is to the protective effect of palladium film.
Embodiment 1
Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour aluminium powder (0.3g) into, cross after dissolving and filters impurity.Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour Ludox (4.6ml) into, cross after dissolving and filters impurity.Silicon solution is poured into rapidly in aluminum solutions, mixes, stirred at ambient temperature 10 hours, obtained molecular sieve preparation liquid.
Palladium film pretreatment: the palladium-based composite membrane prepared is placed on pH and soaks after 15 minutes in the diluted hydrochloric acid aqueous solution of 6.3, washing is to neutral, and in baking oven, 150 DEG C of dryings 4 hours are for subsequent use.
Hydrothermal Synthesis process is as follows: poured into by above-mentioned preparation liquid in Reactive Synthesis still, and the palladium-based composite membrane prepared is loaded in reactor, reactor rotates with the speed of 6 revs/min in homogeneous reactor, be warming up to 90 DEG C simultaneously, continue rotating water thermal synthesis 3 hours, Temperature fall after end of synthesis, after taking-up by washed with de-ionized water to neutral, 150 DEG C of dryings 4 hours.
After low-kappa number, on palladium-based composite membrane, once Hydrothermal Synthesis successfully prepares the molecular screen membrane of even compact, and its surface topography as shown in Figure 4.
Embodiment 2
Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour aluminium powder (0.3g) into, cross after dissolving and filters impurity.Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour Ludox (4.6ml) into, cross after dissolving and filters impurity.Silicon solution is poured into rapidly in aluminum solutions, mixes, stirred at ambient temperature 10 hours, obtained molecular sieve preparation liquid.
Hydrothermal Synthesis process is as follows: poured into by above-mentioned preparation liquid in Reactive Synthesis still, and the palladium-based composite membrane prepared is loaded in reactor, reactor rotates with the speed of 6 revs/min in homogeneous reactor, be warming up to 90 DEG C simultaneously, continue rotating water thermal synthesis 3 hours, Temperature fall after end of synthesis, after taking-up by washed with de-ionized water to neutral, 150 DEG C of dryings 4 hours.
Without low-kappa number, on metal palladium-based composite membrane, once Hydrothermal Synthesis successfully prepares molecular screen membrane, but compared with the molecular screen membrane after acid treatment, surface roughness is comparatively large, and its surface topography as shown in Figure 5.
Embodiment 3
Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour aluminium powder (0.3g) into, cross after dissolving and filters impurity.Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour Ludox (4.6ml) into, cross after dissolving and filters impurity.Silicon solution is poured into rapidly in aluminum solutions, mixes, stirred at ambient temperature 10 hours, obtained molecular sieve preparation liquid.
One time Hydrothermal Synthesis process is as follows: poured into by above-mentioned preparation liquid in Reactive Synthesis still, and the palladium-based composite membrane prepared is loaded in reactor, reactor rotates with the speed of 6 revs/min in homogeneous reactor, be warming up to 90 DEG C simultaneously, continue rotating water thermal synthesis 3 hours, Temperature fall after end of synthesis, after taking-up by washed with de-ionized water to neutral, 150 DEG C of dryings 4 hours.
Intermediate water thermal synthesis: the palladium film obtained after said process terminates is soak 15 minutes in the dilute hydrochloric acid solution of 6.3 in pH value, then repeats above-mentioned Hydrothermal Synthesis step, obtains counterdie-palladium film-molecular screen membrane three-decker composite membrane.Observe pattern and the thickness of molecular screen membrane with SEM characterization method, this composite film surface pattern is shown in Fig. 6.Contrast with the Molecular Sieve Morphology reported in document, the molecular screen membrane on this composite membrane known is hydroxysodalite structure.The molecular screen membrane even compact that palladium-based composite membrane grows, and along with the concavo-convex growth on palladium film surface, tight with palladium film surface conjunction.
Embodiment 4
Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour aluminium powder (0.3g) into, cross after dissolving and filters impurity.Get NaOH (11.1g) and deionized water (50g) is mixed into NaOH solution, pour Ludox (4.6ml) into, cross after dissolving and filters impurity.Silicon solution is poured into rapidly in aluminum solutions, mixes, stirred at ambient temperature 10 hours, obtained molecular sieve preparation liquid.
The palladium copper composite membrane of non-alloying being placed on pH soaks after 15 minutes in the diluted hydrochloric acid aqueous solution of 6.3, washing is to neutral, in baking oven, 150 DEG C of dryings 4 hours are for subsequent use, the preparation method of this palladium copper composite membrane is shown in patent " a kind of composition metal palladium film or alloy palladium film and preparation method thereof ", application number 200410021025, but what the present embodiment used is the palladium copper composite membrane of non-alloying, this palladium film surface completely cover by copper film, i.e. molecular screen membrane growth in situ on fine copper film.
Hydrothermal Synthesis process is as follows: poured into by above-mentioned preparation liquid in Reactive Synthesis still, and the palladium copper composite membrane after above-mentioned dilute acid pretreatment loads in reactor, reactor rotates with the speed of 6 revs/min in homogeneous reactor, be warming up to 90 DEG C simultaneously, continue rotating water thermal synthesis 3 hours, Temperature fall after end of synthesis, after taking-up by washed with de-ionized water to neutral, 150 DEG C of dryings 4 hours.
Through low-kappa number, on the palladium copper composite membrane of non-alloying, once Hydrothermal Synthesis successfully prepares molecular screen membrane, but this molecular screen membrane is continuously uneven, and be combined not tight with palladium copper composite membrane, easily come off, its surface topography as shown in Figure 7.
Embodiment 5
Counterdie-palladium film-molecular screen membrane three-decker composite membrane prepared in embodiment 1 and embodiment 3 and a pure palladium film without molecular screen membrane are loaded in stainless steel reactor, at N after sealing
2(150ml/min), under atmosphere, be warming up to 450 DEG C with the speed of 2 DEG C/min, switch to H
2(300ml/min) be 450 DEG C in temperature after, pressure is activate 96 hours under 0.5MPa, at 450 DEG C, measures the initial permeated hydrogen amount of palladium film under 0.1Mpa condition.Then N is switched to
2(150ml/min) atmosphere is cooled to 300 DEG C after purging 4 hours.Survey the saturating nitrogen quantity under 300 DEG C and 0.5Mpa, then switch to 75%H
2/ N
2pressure is also risen to 0.8Mpa by gaseous mixture (200ml/min), start after stablizing 30 minutes to lower the temperature with the speed of 2 DEG C/min, after temperature is down to 150 DEG C, under the condition that maintenance is temperature-resistant, dropping force to 0.5,0.3 and 0.1MPa, and then pressure is risen to 0.3,0.5 and 0.8MPa, often become a pressure condition and stablize 30 minutes, then under pressure keeps the condition that 0.8MPa is constant, temperature is warming up to 300 DEG C with the speed of 2 DEG C/min, the change of Real-Time Monitoring infiltration gas hydrogen purity in whole process.N is switched to after experiment terminates
2(150ml/min) purge and by Pressure Drop to 0.5MPa, at 300 DEG C after 10 hours, under 0.5MPa condition, measure the saturating nitrogen quantity of palladium film.This hydrogen embrittlement experimental result sees the following form, and the saturating nitrogen quantity of palladium film refers to the transit dose of palladium film to nitrogen, and the ability of saturating nitrogen quantity larger explanation palladium film Selective Separation hydrogen is poorer.Visible, under similarity condition, nitrogen quantity change is less thoroughly after the circulation of experience temperature and pressure for counterdie-palladium film-molecular screen membrane three-decker composite membrane, the saturating nitrogen quantity of the composite membrane after a Hydrothermal Synthesis increases by 4 times, the saturating nitrogen quantity of composite membrane after intermediate water thermal synthesis is substantially constant, and counterdie-palladium film double-layer structure composite membrane saturating nitrogen quantity after the circulation of experience temperature and pressure adds 21 times, illustrate that there occurs Hydrogen Brittleness Phenomena causes film to lose the selective ability through hydrogen.
Embodiment 6
According to preparation method described in embodiment 3, the intermediate water thermal synthesis time is increased to 6 hours, obtain the film pipe of palladium film-molecular screen membrane-6h, film pipe prepared by embodiment 3 is defined as palladium film-molecular screen membrane-3h, at 400 DEG C, under passing into the condition of 5% propylene/hydrogen mixed gas of flow 200ml/min under 0.2MPa pressure, the permeated hydrogen amount of Real-Time Monitoring pure palladium film and above-mentioned two film pipes, measure propylene to the impact of the permeated hydrogen amount of different palladium film, result is illustrated in fig. 8 shown below.Permeated hydrogen amount with or without the palladium film of molecular screen membrane protection all passes into the time along with propylene and declines; the permeated hydrogen amount fall off rate of pure palladium film is 3.4 times of the palladium film having molecular screen membrane to protect; and the Hydrothermal Synthesis time of molecular sieve is longer; the protective effect of molecular screen membrane to palladium film is more obvious, and the Hydrothermal Synthesis molecular screen membrane permeated hydrogen amount fall off rate of 3 hours is 3.1 times of the Hydrothermal Synthesis molecular screen membrane of 6 hours.Because the molecular dynamics diameter of propylene is 0.39nm, and the molecular sieve of hydroxysodalite structure prepared by this method belongs to 4A molecular sieve, and aperture is 0.4nm.Therefore; under 5% propylene/hydrogen mixed gas atmosphere; the action principle of 4A molecular screen membrane protection palladium film be by propylene adsorbs in the duct of molecular screen membrane; thus suppress propylene on the impact of palladium film permeated hydrogen amount; molecular screen membrane is thicker; stronger to the protective effect of palladium film, more can extend the service life of palladium film.Molecular dynamics diameter is greater than to other foreign gases of 0.4nm, molecular screen membrane can stop foreign gas contact palladium film, and molecular screen membrane is finer and close, stronger to the protective effect of palladium film, more can extend the service life of palladium film.
The crack damage that membrane structure of the present invention can suppress palladium film generation deformation to cause, improves palladium film anti-hydrogen embrittlement performance under cryogenic, extends the service life of palladium film.In addition, utilize molecular screen membrane to the sieve performance of molecule, adsorbable or stop foreign gas contacts with palladium film, suppresses it to the toxic action of palladium film.The inventive method is that palladium base hydrogen separation membrane provides a kind of anti-hydrogen embrittlement and anti-poisoning safeguard procedures, extends the scope of application and the service life of palladium film, will obtain extensive use.
Claims (10)
1. a method for molecular screen membrane is prepared on Metal Palladium film surface, it is characterized in that being obtained by following steps:
1) on porous counterdie, palladium film is prepared;
2) palladium film diluted acid is carried out surface treatment;
3) the palladium film after process is placed in the reactor that Zeolite synthesis liquid is housed, at 80-150 DEG C, synthesizes 1-15 hour, synthesis number of times is 1-5 time, and the superficial growth of palladium film goes out molecular screen membrane;
4) composite membrane of counterdie-palladium film-molecular screen membrane three-decker is obtained after molecular screen membrane being washed till neutrality.
2. method according to claim 1, is characterized in that: described palladium film diluted acid is carried out surface treatment process, and the diluted acid of employing is any one in watery hydrochloric acid and dust technology; The pH value of diluted acid controls between 5.5-6.8, and optimal pH is 6.3; Dilute acid pretreatment time controling is at 5-60 minute, and the optimization process time is 15 minutes.
3. method according to claim 1, it is characterized in that: the described molecular sieve precursor solution used at palladium film surface synthesizing molecular sieve film is mixed by aluminum feedstock, silicon raw material and alkali, aluminum feedstock is the one in metallic aluminium, sodium metaaluminate, sodium aluminate, aluminum sulfate, silicon raw material is Ludox or sodium metasilicate, alkali is NaOH or potassium hydroxide, is: SiO with the mol ratio of oxide basis
2/ Al
2o
3=2-100, H
2o/Al
2o
3=100-2000, Na
2o/Al
2o
3=2-100, optimizing mol ratio is: SiO
2/ Al
2o
3=2-10, H
2o/Al
2o
3=200-1000, Na
2o/Al
2o
3=10-60.
4. the method according to claim 1 or 3, is characterized in that: at Metal Palladium film surface in situ growth molecular screen membrane, molecular screen membrane can adopt hydro-thermal method or microwave method;
Described water heat transfer molecular sieve adopts homogeneous reactor, and synthesis condition is temperature 80-150 DEG C, and the time is 1-15 hour, and synthesis number of times is 1-5 time;
Described microwave method synthesis of molecular sieve adopts microwave reactor, and synthesis condition is temperature 80-100 DEG C, and the time is 5-60 minute, and synthesis number of times is 1-5 time.
5. method according to claim 1, is characterized in that: counterdie is porous supporting body, can be any one in porous ceramics, porous metals, cellular glass; Palladium film is pure palladium film or palladium alloy membrane (wherein the molar content of palladium is 20-100%), alloy film can be palladium-silver, palladium copper, porpezite, palladium-nickel alloy film any one; Molecular screen membrane is the porous material with molecule screening function, comprise zeolite molecular sieve film and Carbon Molecular Sieve Membrane, molecular screen membrane can be any one in the molecular sieve of LTA type (comprising 3A, 4A, 5A type molecular sieve), FAU type (comprising X, Y zeolite), MFI type.
6. method according to claim 1, is characterized in that: describedly on porous counterdie, prepare palladium film, and can adopt any one in chemical plating, chemical vapour deposition technique, physical vaporous deposition, galvanoplastic, sputtering method, thickness is 2-20 μm; The method optimizing palladium plated film is chemical plating, and optimization thickness is 7-9 μm.
7. the composite membrane of superimposed successively counterdie-palladium film-molecular screen membrane three-decker prepared of a claim 1-6 either method.
8. an application for composite membrane described in claim 7, is characterized in that: during the composite membrane separating hydrogen gas of described counterdie-palladium film-molecular screen membrane three-decker, hydrogen be from molecular screen membrane side through palladium film thoroughly to counterdie side.
9. the application of composite membrane according to claim 8, is characterized in that: the service condition of described composite membrane is 80-500 DEG C, and pressure is 0.1-10MPa.
10. the application of composite membrane according to claim 8 or claim 9, it is characterized in that: when composite membrane carries out Hydrogen Separation from gaseous mixture, in gaseous mixture, hydrogen molar concentration is 50-99.99%; In gaseous mixture, remaining gas is one or two or more kinds in nitrogen, carbon monoxide, carbon dioxide, methane, the alkane of C2-C7 or alkene.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108014648A (en) * | 2016-10-31 | 2018-05-11 | 中国科学院大连化学物理研究所 | A kind of method for preparing double-deck palladium-based composite membrane |
| CN108079797A (en) * | 2018-01-02 | 2018-05-29 | 兰州理工大学 | A kind of preparation method of hydrogen palladium alloy composite membrane |
| CN109824627A (en) * | 2019-03-01 | 2019-05-31 | 山东理工大学 | A kind of method of the saturating hydrogen coupled film microreactor synthesizing epoxypropane of oxygen flow |
| CN109876745A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | The palladium copper composite film material of load TS -1 molecular sieve and preparation and application |
| CN109957772A (en) * | 2017-12-26 | 2019-07-02 | 北京有色金属研究总院 | A kind of palladium/ceramic composite film |
| CN110681270A (en) * | 2019-09-29 | 2020-01-14 | 天津大学 | Preparation method of sandwich type MFI molecular sieve membrane on different carriers and alcohol application of membrane |
| CN110903265A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院大连化学物理研究所 | Method for carrying out gas phase propylene epoxidation reaction in palladium membrane reactor |
| CN110913979A (en) * | 2017-07-18 | 2020-03-24 | 诺和锐驰科技有限责任公司 | Zeolite supported molecular sieve membrane |
| WO2021194417A1 (en) * | 2020-03-23 | 2021-09-30 | National University Of Singapore | A palladium-based membrane |
| CN114011372A (en) * | 2021-11-30 | 2022-02-08 | 齐鲁工业大学 | Bifunctional microstructure palladium-based membrane reactor and preparation method thereof |
| CN114634162A (en) * | 2020-12-15 | 2022-06-17 | 南京工业大学 | Hydrogen purification process adopting CHA type molecular sieve membrane |
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| CN108014648A (en) * | 2016-10-31 | 2018-05-11 | 中国科学院大连化学物理研究所 | A kind of method for preparing double-deck palladium-based composite membrane |
| CN110913979B (en) * | 2017-07-18 | 2022-03-22 | 诺和锐驰科技有限责任公司 | Zeolite supported molecular sieve membrane |
| CN110913979A (en) * | 2017-07-18 | 2020-03-24 | 诺和锐驰科技有限责任公司 | Zeolite supported molecular sieve membrane |
| CN109876745A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | The palladium copper composite film material of load TS -1 molecular sieve and preparation and application |
| CN109957772A (en) * | 2017-12-26 | 2019-07-02 | 北京有色金属研究总院 | A kind of palladium/ceramic composite film |
| CN108079797A (en) * | 2018-01-02 | 2018-05-29 | 兰州理工大学 | A kind of preparation method of hydrogen palladium alloy composite membrane |
| CN110903265A (en) * | 2018-09-14 | 2020-03-24 | 中国科学院大连化学物理研究所 | Method for carrying out gas phase propylene epoxidation reaction in palladium membrane reactor |
| CN109824627A (en) * | 2019-03-01 | 2019-05-31 | 山东理工大学 | A kind of method of the saturating hydrogen coupled film microreactor synthesizing epoxypropane of oxygen flow |
| CN109824627B (en) * | 2019-03-01 | 2023-08-29 | 山东理工大学 | Method for synthesizing epoxypropane by oxygen-permeable and hydrogen-permeable coupling membrane microreactor |
| CN110681270A (en) * | 2019-09-29 | 2020-01-14 | 天津大学 | Preparation method of sandwich type MFI molecular sieve membrane on different carriers and alcohol application of membrane |
| CN110681270B (en) * | 2019-09-29 | 2021-11-05 | 天津大学 | Preparation method of sandwich type MFI molecular sieve membrane on different carriers and alcohol application of membrane |
| WO2021194417A1 (en) * | 2020-03-23 | 2021-09-30 | National University Of Singapore | A palladium-based membrane |
| CN114634162A (en) * | 2020-12-15 | 2022-06-17 | 南京工业大学 | Hydrogen purification process adopting CHA type molecular sieve membrane |
| CN114011372A (en) * | 2021-11-30 | 2022-02-08 | 齐鲁工业大学 | Bifunctional microstructure palladium-based membrane reactor and preparation method thereof |
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