CN101134158B - Compound film for separating hydrogen gas and method for preparing the same and the hydrogen gas segregator - Google Patents
Compound film for separating hydrogen gas and method for preparing the same and the hydrogen gas segregator Download PDFInfo
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- CN101134158B CN101134158B CN2006101276141A CN200610127614A CN101134158B CN 101134158 B CN101134158 B CN 101134158B CN 2006101276141 A CN2006101276141 A CN 2006101276141A CN 200610127614 A CN200610127614 A CN 200610127614A CN 101134158 B CN101134158 B CN 101134158B
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Abstract
The composite film for separating hydrogen includes a support layer of porous material, a middle non-diffusing layer and a hydrogen penetrating alloy film layer arranged successively. The support layer of porous metal or alloy material and the middle non-diffusing layer of oxide of the metal or alloy form one integral structure. The present invention also provides also the preparation process of the composite film and one hydrogen separator with the composite film. The composite film for separating hydrogen has simple preparation process, excellent combination of the support layer and the middle non-diffusing layer in integral structure and less breaking caused by deformation.
Description
Technical field
The invention relates to a kind of composite membrane that is used for separating hydrogen gas and preparation method thereof and the hydrogen gas segregator that uses this composite membrane.
Background technology
Be applied to fields such as fuel cell, semi-conductor industry, petrochemical industry refining more and more along with hydrogen, the demand of hydrogen constantly increases, and hydrogen will play more and more important effect in the clean energy resource economy in future.The main source of hydrogen is rich hydrogen gaseous mixture, the molar concentration of hydrogen is generally 40-60% in the rich hydrogen gaseous mixture, what also contain 1-3% simultaneously has the CO of passivation to electrode catalyst of fuel cell, but the application of a lot of hydrogen all requires the higher hydrogen of purity, for example, pure hydrogen is the optimal energy carrier of fuel cell, and other composition of rich hydrogen gaseous mixture may react by passivated electrodes, reduces the power density of fuel cell.
Therefore, before using, generally all need rich hydrogen gaseous mixture is separated, to obtain high-purity hydrogen.The most simple and effective separation method is with the alternative film that sees through hydrogen rich hydrogen gaseous mixture to be carried out film to separate.
The alternative film that sees through hydrogen can be divided into four classes: polymeric membrane, porous ceramic film, no support metal film, the support metal film is arranged.In the four class films, polymeric membrane is not high to the selectivity of hydrogen, and the purity of separating the hydrogen obtain is not high, and such polymeric membrane can not be used for the environment more than 250 ℃, and the carbohydrate in the gaseous mixture also can reduce its separating effect.There are problems such as selectivity is low, frangible in porous ceramic film.These problems make the application of above-mentioned two class films be restricted.To obtain applicable highly purified hydrogen in order separating, generally to select no support metal film for use or the support metal film is arranged.
Therefore people find that very early the palladium film has the characteristics of good selective permeation to hydrogen, and the research to the metal film that is used for separating hydrogen gas mainly concentrates on palladium and alloy film thereof.When hydrogen contact palladium or palladium alloy membrane, hydrogen molecule will be dissociated into hydrogen atom on the surface of film, and hydrogen atom can spread in film gradually, arrives another surface of palladium film, hydrogen atom recombines into hydrogen molecule on this surface then, thereby reaches the purpose of separating hydrogen gas.
Because fully in the metal film of making by Metal Palladium, along with the difference of hydrogen content, the lattice of palladium can α mutually and β change between mutually.The lattice structure of β phase is than the lattice structure volumetric expansion 3% of α phase, so after changing for several times between the two-phase, the palladium film is because the inner stress effect that constantly stretches, compresses, be easy to just occur embrittlement, the performance failure that causes its selective permeation hydrogen, so the general complete metal film of being made by Metal Palladium is applicable to that temperature is higher than 300 ℃, pressure is greater than 20 atmospheric environment.
A way that addresses the above problem is exactly the palladium alloy membrane that utilizes palladium and other metal to form.McKinley discloses a kind of effective palladium alloy membrane PdAu film in its patent US 3350845, disclose the PdCu alloy film again in its patent US 3439474 afterwards.Above-mentioned alloy film not only can solve the problem that changes embrittlement because of lattice, has also improved hydrogen by the speed (oozing hydrogen speed) of film with to CO, H simultaneously
2The tolerance of materials such as S has reduced the consumption of precious metal palladium simultaneously.The thickness of above-mentioned alloy film is generally the 20-100 micron.
Common palladium alloy membrane is PdAg, PdCu, PdAu alloy film etc. now.These alloy films can be divided into the alloy film of alloy film that supporter is arranged and no supporter according to its supporting construction.No supporter is meant under the alloy film does not have backing material, and alloy film becomes a separating slices or tubular structure separately.In actual separation, film need bear the pressure of required expansion of separating hydrogen gas or compression, and it is very thick that this just makes that the alloy film of this no supporter need be done, and oozes hydrogen speed and thickness is inversely proportional to, therefore do not have supporter alloy film to ooze hydrogen speed also lower, need bigger membrane area.Increase in the time of membrane area and thickness, shared volume increases, and increases manufacturing cost simultaneously.
Therefore, people tend to develop the alloy film of supporter, ooze hydrogen speed to reduce the thickness of alloy film, to improve, and supporter is generally by Al
2O
3, the pottery, SiO
2, porous material such as porous metals makes.For example, CN 1117941A discloses a kind of methanol steam reforming hydrogen manufacturing reactor with ceramic-metal composite film, and described ceramic-metal composite film comprises ceramic parent tube and is plated in PdAg alloy film on the ceramic parent tube by chemical plating.But utilize Al
2O
3, the pottery, SiO
2There is a potential shortcoming as supporter, the hot expansion system of these porous materials differs greatly with metal, and its loose structure is originally under repeatedly temperature, pressure change, because of the skewness of internal stress, be easy to embrittlement, ceramic material also is difficult for and other position combination seal in addition.
In order to solve the shortcoming of the easy embrittlement of backing material such as above-mentioned pottery, can utilize porous metal material as supporter, as the porous stainless steel material.Porous metal material all has good performance at aspects such as hardness, resistance to compressions, but, under higher temperature, the atom of alloy film can spread in the porous metal material as supporter gradually, the atom of porous metal material also can cause the transmission rates of hydrogen to descend gradually to the alloy film diffusion into the surface simultaneously.The speed of atom phase counterdiffusion can reach maximum between two kinds of metals when temperature is equal to or higher than its Tamman temperature, because reach after this temperature, can cause sizable thermal vibration between lattice.The Tamman temperature be generally its melting point metal temperature half (measure with kelvin degree, K), Tamman temperature as palladium is 913K (640 ℃), stainless steel is 823-833K (550-560 a ℃), so temperature is higher than 550 ℃, iron atom can be diffused in the palladium alloy membrane gradually, reduces it and oozes hydrogen speed.
In order to eliminate or to reduce the intermetallic phase counterdiffusion, can in the middle of porous metals supporter and alloy film, add heat-staple intermediate layer.For example, US 5259870 discloses a kind of hydrogen permeability composite metal membrane, this composite metal membrane comprises hydrogen permeability underlying metal, hydrogen permeability coating metal and the middle barrier layer between the two, and described middle barrier layer is selected from by the oxide of aluminium, lanthanum, molybdenum, silicon, tungsten and yttrium and the sulfide of molybdenum, tungsten and vanadium.This composite metal membrane is preferably by making three kinds of constituent laminations.Middle barrier layer preferably chemically is applied on the underlying metal by depositing inorganic oxide or sulfurized layer.When middle barrier layer was oxide, to underlying metal, hydrolysis formed oxide skin(coating) then with solution spraying, rotation coating or the dip coated of oxide precursor.When middle barrier layer is metal sulfide, under high-temperature and high-pressure conditions, underlying metal is exposed a period of time such as 5-15 minute in sulfide gas such as hydrogen sulfide; Perhaps with the solution spraying of sulfide precursor, rotation coating or dip coated to underlying metal, form sulfurized layer with the hydrogen sulfide reaction then.The other method that applies oxide or sulfurized layer be with oxide or sulfide vapour deposition to underlying metal.Because metal sulfide less stable under hot conditions is easy to decompose, and influences the transmission rates of hydrogen.Therefore, the general metal oxide that uses is as middle barrier layer, but the existing preparation metal oxide is as the method complexity of middle barrier layer, and combining between the metal oxide that obtains and the underlying metal is bad, be easy to generate stress between the two and make metal oxide generation deformation, thereby outermost hydrogen permeability coating metal is broken easily.
Summary of the invention
The objective of the invention is provides the composite membrane that a kind of preparation method is simple and be difficult for breaking in order to overcome the existing complicated and crackly shortcoming of preparation method that is used for the composite membrane of separating hydrogen gas.
The hydrogen gas segregator that another object of the present invention provides the preparation method of this composite membrane that is used for separating hydrogen gas and uses this composite membrane.
The invention provides a kind of composite membrane that is used for separating hydrogen gas, this composite membrane comprises porous material supporting layer 101, middle barrier layer 102 and the alloy hydrogen permeation membrane layer 103 that forms successively, wherein, described porous material supporting layer 101 is a metal or metal alloy, middle barrier layer 102 is the oxide of described porous material supporting layer metal or metal alloy, and porous material supporting layer 101 and middle barrier layer 102 are structure as a whole.
The invention provides a kind of preparation method who is used for the composite membrane of separating hydrogen gas, the surface that this method is included in the porous material supporting layer forms middle barrier layer, form alloy hydrogen permeation membrane layer on the surface of middle barrier layer then, wherein, described porous material supporting layer is a metal or metal alloy, and the method for barrier layer is oxidized to metal oxide for the metal or metal alloy with the porous material support layer surface in the middle of forming on the surface of porous material supporting layer.
The invention provides a kind of hydrogen gas segregator, this hydrogen gas segregator comprises that seeing through chamber 202, hydrogen collection chamber 203, rich hydrogen gaseous mixture inlet 201, hydrogen outlet 204 and residual gas by the compound film formed hydrogen selective that is used for separating hydrogen gas exports 205, hydrogen selective sees through chamber 202 and is arranged in hydrogen collection chamber 203, rich hydrogen gaseous mixture inlet 201 and residual gas outlet 205 see through chamber 202 with hydrogen selective and are communicated with, hydrogen outlet 204 is communicated with hydrogen collection chamber 203, wherein, the composite membrane that is used for separating hydrogen gas is a composite membrane provided by the invention.
According to the composite membrane that is used for separating hydrogen gas provided by the invention, the surface oxidation of porous material supporting layer becomes metal oxide layer as middle barrier layer, preparation method is simple, because porous material supporting layer and middle barrier layer are structure as a whole, between the two in conjunction with fine, the deformation that caused by stress can not take place, so composite membrane is difficult for breaking.
Description of drawings
Fig. 1 and 2 is the cross section structure schematic diagram that is used for the composite membrane of separating hydrogen gas provided by the invention;
Fig. 3 and 4 is the structural representation of hydrogen gas segregator provided by the invention.
The specific embodiment
The composite membrane that is used for separating hydrogen gas provided by the invention from inside to outside comprises porous material supporting layer 101, middle barrier layer 102 and alloy hydrogen permeation membrane layer 103 successively, wherein, described porous material supporting layer 101 is a metal or metal alloy, middle barrier layer is the oxide of 102 described porous material supporting layer metal or metal alloy, and porous material supporting layer 101 and middle barrier layer 102 are structure as a whole.
Porous material supporting layer 101 can have only middle barrier layer 102 is arranged on the surface, also can on two surfaces middle barrier layer 102 be arranged all.When porous material supporting layer 101 has only middle barrier layer 102 is arranged on the surface, in the middle of alloy hydrogen permeation membrane layer 103 is positioned at barrier layer 102 not with surface that porous material supporting layer 101 contacts on; When middle barrier layer 102 is all arranged on 101 two surfaces of porous material supporting layer, alloy hydrogen permeation membrane layer 103 can only be positioned at barrier layer 102 in the middle of not with surface that porous material supporting layer 101 contact on, also can be positioned at two centre barrier layers 102 not with surface that porous material supporting layer 101 contacts on.
As shown in Figure 1, porous material supporting layer 101 has only middle barrier layer 102 is arranged on the surface, in the middle of alloy hydrogen permeation membrane layer 103 is positioned at barrier layer 102 not with surface that porous material supporting layer 101 contacts on.As shown in Figure 2, the porous material supporting layer all has middle barrier layer 102 on 101 two surfaces, alloy hydrogen permeation membrane layer 103 be positioned at barrier layers 102 in the middle of two not with surface that porous material supporting layer 101 contacts on.
Described porous material supporting layer can be a kind of metal in iron, aluminium, the magnesium, perhaps is the alloy of two kinds or two kinds metals in iron, aluminium, the magnesium, is preferably stainless steel.Wherein the average pore diameter of porous material supporting layer, porosity and thickness have been conventionally known to one of skill in the art.In the present invention, the average pore diameter of porous material supporting layer is preferably the 0.01-2 micron, more preferably the 0.01-1 micron; Thickness is preferably the 0.1-3 millimeter, more preferably the 0.1-2 millimeter; Porosity is preferably 20-50%, more preferably 35-45%.Porosity described herein is the ratio of the surface area of shared area of micropore and porous material supporting layer.Described porous material supporting layer is preferably tubulose, and the composite membrane that makes thus also is tubulose, can directly see through chamber as hydrogen selective.The composite membrane of tubulose from inside to outside comprises porous material supporting layer 101, middle barrier layer 102 and alloy hydrogen permeation membrane layer 103 successively.
Middle barrier layer is the oxide of described porous material supporting layer metal or metal alloy, can be the oxide of a kind of metal in iron, aluminium, the magnesium, perhaps is the oxide of the alloy of two kinds or two kinds metals in iron, aluminium, the magnesium, is preferably iron oxide.The integrative-structure of middle barrier layer and porous material supporting layer can be by realizing the surface oxidation of porous material supporting layer.The thickness of middle barrier layer is the 5-20 micron, is preferably the 5-15 micron; Average pore diameter is the 0.01-0.1 micron, is preferably the 0.02-0.08 micron.
Alloy hydrogen permeation membrane layer has been conventionally known to one of skill in the art, and for example, alloy hydrogen permeation membrane layer can be the alloy of palladium and other transition metal, and in the present invention, alloy hydrogen permeation membrane layer is preferably palladium-silver, palladium-copper alloy or Polarium.In alloy hydrogen permeation membrane layer, be benchmark with the gross weight of alloy, the content 40-90 weight % of palladium is preferably 40-60 weight %.The thickness of alloy hydrogen permeation membrane layer can be the 0.5-25 micron, is preferably the 0.5-15 micron, more preferably the 1-10 micron.
In the present invention, the thickness of porous material supporting layer, middle barrier layer and alloy hydrogen permeation membrane layer can adopt the method for ESEM to measure.
Barrier layer in the middle of the surface that the preparation method who is used for the composite membrane of separating hydrogen gas provided by the invention is included in the porous material supporting layer forms, form alloy hydrogen permeation membrane layer on the surface of middle barrier layer then, wherein, described porous material supporting layer is a metal or metal alloy, and the method for barrier layer is oxidized to metal oxide for the metal or metal alloy with the porous material support layer surface in the middle of forming on the surface of porous material supporting layer.
The metal or metal alloy of porous material support layer surface is oxidized to metal oxide comprises the porous material supporting layer is contacted with oxidizing gas that it is the metal oxide of 5-20 micron that the condition of contact and the consumption of oxidizing gas are enough to make the porous material support layer surface to form thickness.
Wherein, the condition of described contact comprise the contact temperature be 300 ℃ to less than the temperature of porous material supporting layer metal or metal alloy fusing point, be 6-12 hour time of contact; The theoretical consumption of the oxidizing gas of the metal oxide that the consumption of oxidizing gas is not less than and makes described metal formation thickness is the 5-20 micron.
Can determine the contact temperature according to the metal ingredient of employed porous material supporting layer, as long as the contact temperature is lower than the fusing point of porous material supporting layer metal or metal alloy.For example, if elect stainless steel material as, then contact temperature and be preferably 400-900 ℃, more preferably 400-600 ℃ as the porous material supporting layer.Can determine the consumption of time of contact and oxidizing gas according to the thickness of middle barrier layer, can be 6-12 hour time of contact, is preferably 8-10 hour; The thickness of barrier layer was the 5-20 micron in the middle of the consumption of oxidizing gas was enough to make, and was preferably the 5-15 micron.Oxidizing atmosphere is the gas that contains oxygen, is preferably the gaseous mixture of oxygen and nitrogen, and the volume ratio of oxygen and nitrogen is 1: 9 to 9: 1, is preferably 1: 5 to 5: 1.
Pore size and pore size distribution for barrier layer in the middle of optimizing, under the preferable case, with before oxidizing gas contacts, the temperature of porous material supporting layer is slowly risen to the contact temperature from room temperature at the porous material supporting layer, and after having contacted, from contacting the temperature quenching to normal temperature.For example, can in 1-5 hour, preferably in 2-4 hour the temperature of porous material supporting layer be risen to the temperature of contact from room temperature; With after oxidizing gas contacts, in 5-20 minute, the temperature of the porous material supporting layer of barrier layer is reduced to 50-100 ℃ from the temperature of contact in the middle of the surface being formed with in preferred 10-15 minute with the porous material supporting layer.
Before the barrier layer, this method can also comprise the cleaning porous material in the middle of forming.The process of cleaning porous material comprises porous material in alkaline solution supersound washing 3-5 hour; Spend deionised water to the pH of flushing liquor be 7; Deionized water for ultrasonic washing 1-5 time, washed 0.5-2 hour at every turn; With the moisture in the isopropyl alcohol cleaning micropore, dry then.The used hyperacoustic power of supersound washing can be 100-200 watt, is preferably 150-200 watt.Described alkaline solution is preferably the aqueous solution that contains alkaline matter and washing agent, described alkaline matter can be any alkaline matter that does not corrode porous material, for example, can be in sodium phosphate, sodium carbonate, NaOH, potassium phosphate, potash and the potassium hydroxide one or more, the content of alkaline matter can be the 20-200 grams per liter, is preferably the 50-180 grams per liter; Washing agent can be the commercially available liquid detergent of routine, the content of washing agent be the 1-20 milliliter/liter, be preferably the 3-15 milliliter/liter.The organic dirt of porous material support layer surface can be further removed in cleaning, is convenient to barrier layer in the middle of porous material support layer surface original position forms.
The method that forms alloy hydrogen permeation membrane layer on the surface of middle barrier layer has been conventionally known to one of skill in the art, can adopt chemical plating, plating, chemical vapour deposition (CVD), physical vapour deposition (PVD).Chemical plating and plating are fairly simple, implement easily, still are difficult to control the composition and the thickness of alloy hydrogen permeation membrane layer.Chemical vapour deposition (CVD) is very strict to the requirement of purity of raw materials and depositional environment, is not easy to implement.Physical vapour deposition (PVD) can accurately be controlled the composition and the thickness of alloy hydrogen permeation membrane layer, and easy to operate, and therefore, the present invention preferably adopts physical vaporous deposition to form alloy hydrogen permeation membrane layer.
Physical vapour deposition (PVD) is mainly magnetron sputtering method, and magnetron sputtering method is included under the sputtering condition target as sputter is arrived substrate surface.In the present invention, described target is the metal of component alloy hydrogen permeation membrane layer, and base material is formed with the porous material supporting layer of middle barrier layer for the surface.Described sputtering condition can be the sputtering condition of routine, and in the present invention, sputtering condition comprises that the distance between target and the base material is 5-20 centimetre, and base material temperature is 300-500 ℃, and the velocity of rotation of base material is 15-25 rev/min, and back of the body end vacuum is 3 * 10
-5To 9 * 10
-5Handkerchief, sputtering pressure are the 0.1-1 handkerchief, and sputtering atmosphere is an inert gas, and sputtering power is 10-200 watt, and sputtering time is 1-5 hour.After the sputter, can be under nitrogen, nitrogen hydrogen mixeding gas or argon shield, in the target molten alloyization that forms on substrate surface under 600-900 ℃.
Hydrogen gas segregator provided by the invention comprises that seeing through chamber 202, hydrogen collection chamber 203, rich hydrogen gaseous mixture inlet 201, hydrogen outlet 204 and residual gas by the compound film formed hydrogen selective that is used for separating hydrogen gas exports 205, hydrogen selective sees through chamber 202 and is arranged in hydrogen collection chamber 203, rich hydrogen gaseous mixture inlet 201 and residual gas outlet 205 see through chamber 202 with hydrogen selective and are communicated with, and hydrogen outlet 204 is communicated with hydrogen collection chamber 203.
The structure that is used for the composite membrane of separating hydrogen gas is described in detail hereinbefore, does not repeat them here.
See through chamber 202 by the compound film formed hydrogen selective that is used for separating hydrogen gas and can be tubulation, helix tube or panel chamber form.Owing to adopt panel chamber form to need the stack architecture pattern, complexity is installed, therefore generally seldom adopt.As shown in Figure 3, it is the tubulation form that hydrogen selective sees through chamber 202, at this moment, hydrogen gas segregator also comprises gas distribution grid 206 and two end plates 207, gas distribution grid 206 is connected with the sidewall of hydrogen collection chamber 203 is airtight with end plate 207, have the hydrogen selective that can make tubular type to see through the hole that chamber 202 passes on two end plates 207, hydrogen selective passes these holes through chamber 202 and is welded on the end plate; Gas distribution grid 206 sees through chamber 202 with rich hydrogen gaseous mixture inlet 201 and hydrogen selective and communicates, and gas distribution grid 206 can see through the hydrogen selective that is distributed to the tubulation form from the rich hydrogen gaseous mixture inlet 201 rich hydrogen gaseous mixtures that enter the chamber 202.Rich hydrogen gaseous mixture enters into hydrogen selective through chamber 202 from rich hydrogen gaseous mixture inlet 201, and the hydrogen in the rich hydrogen gaseous mixture enters into hydrogen collection chamber 203 through the alternative film that sees through hydrogen and passes through hydrogen outlet 204 discharges; Other gas componant in the rich hydrogen gaseous mixture can not see through the alternative film that sees through hydrogen, discharges from residual gas outlet 205.
Adopt a plurality of tubulations, the hydrogen that separates can be evenly arranged in the hydrogen collection chamber 203, ooze hydrogen speed according to the tubulation total surface, control the air inlet speed of rich hydrogen gaseous mixture, making rich hydrogen gaseous mixture see through in the chamber 202 at hydrogen selective has enough time of staying, therefore can improve the yield of hydrogen.
As shown in Figure 4, hydrogen selective is the helix tube form through chamber 202.Adopt the structure of helix tube, improved volume utilization, rich hydrogen gaseous mixture is seen through in the chamber 202 at hydrogen selective the sufficient time of staying, therefore can improve the yield of hydrogen.
Hydrogen gas segregator provided by the invention in use, rich hydrogen gaseous mixture enters into hydrogen selective through chamber 202 from rich hydrogen gaseous mixture inlet 201, and the hydrogen in the rich hydrogen gaseous mixture enters into hydrogen collection chamber 203 through the alternative film that sees through hydrogen and passes through hydrogen outlet 204 discharges; Other gas componant in the rich hydrogen gaseous mixture can not see through the alternative film that sees through hydrogen, discharges from residual gas outlet 205.
When the preparation composite membrane that is used for separating hydrogen gas of the present invention, the porous material that can adopt tubulose is as supporting layer, and the composite membrane that makes so also is tubulose, can directly see through chamber 202 as hydrogen selective.
The structure and material of other member of hydrogen gas segregator such as hydrogen collection chamber 203, rich hydrogen gaseous mixture inlet 201, hydrogen outlet 204 and residual gas outlet 205 has been conventionally known to one of skill in the art, and for example hydrogen collection chamber 203 can be made by stainless steel material.
Below by embodiment the present invention is described in more detail.
Embodiment 1
This embodiment is used to illustrate composite membrane of the present invention and preparation method thereof.
With length is that 5 centimetres, external diameter are that 10 millimeters, internal diameter are that 7 millimeters, surperficial average pore size are that 0.4 micron, porosity are that 40% porous stainless steel cleans as follows: at 60 ℃ alkaline solution (Na
3PO
430 grams per liters, Na
2CO
365 grams per liters, NaOH 45 grams per liters, 6 milliliters/liter in washing agent) in, with 150 watts ultrasonic washings 1 hour; Deionized water rinsing to the pH of flushing liquor be 7; Use deionized water with 150 watts ultrasonic washing three times, each one hour again; With the moisture in 1000 milliliter 80% the isopropyl alcohol cleaning micropore, 120 ℃ following dry 4 hours then.
In the high temperature furnace that porous stainless steel after the above-mentioned cleaning is sent into, temperature speed with 4 ℃/minute in 2 hours in the high temperature furnace is warming up to 500 ℃ from 20 ℃, feeding excessive volume ratio far away then in high temperature furnace is 4: 1 the oxygen and the mist of nitrogen, and 500 ℃ of following sintering 6 hours, then with porous stainless steel in 15 minutes with-30 ℃/minute speed quenching to 50 ℃, the interior tube-surface of porous stainless steel and outside tube-surface all to form thickness be that 9 microns oxide layer is as middle barrier layer.
Two ports that will be formed with the porous stainless steel of oxide layer are sealed up, and send into the rf magnetron sputtering instrument as base material, carry out two target magnetic control sputterings of Pd, Ag.It is the Ag of 99.99%Pd and 99.99% that target is selected purity for use, and the distance between target and the base material remains on 10 centimetres, and base material temperature is set at 400 ℃, and base material rotates with 20 rev/mins speed at pedestal.Back of the body end vacuum is 6 * 10
-5Handkerchief, sputtering pressure are 0.2 handkerchief, and sputtering atmosphere is 99.999% argon gas, are 125 watts to the sputtering power of Pd, are 25 watts to the sputtering power of Ag.Through three hours sputter, obtain thickness at last and be 5 microns palladium-silver film, palladium is 74: 26 with the weight ratio of silver in this alloy film.Under the nitrogen and hydrogen mixture protection, in 700 ℃ high temperature furnace, cool off after the molten alloyization afterwards, obtain complex film M 1 provided by the invention.
Embodiment 2
This embodiment is used to illustrate composite membrane of the present invention and preparation method thereof.
With helix length is that 5 centimetres, external diameter are that 10 millimeters, internal diameter are that 9.5 millimeters, surperficial average pore size are that 0.8 micron, porosity are that 30% porous stainless steel helix tube cleans as follows: at 80 ℃ alkaline solutions (NaOH 60 grams per liters, 12 milliliters/liter in washing agent) in, with 150 watts ultrasonic washings 1.5 hours; Deionized water rinsing to the pH of flushing liquor be 7; Use deionized water with 150 watts ultrasonic washing 1.5 hours again; Clean the interior moisture of micropore with 1000 milliliter of 80% isopropyl alcohol then, 150 ℃ following dry 2 hours.
Porous stainless steel helix tube after the above-mentioned cleaning is sent in the high temperature furnace, temperature speed with 3 ℃/minute in 4 hours in the high temperature furnace is warming up to 740 ℃ from 20 ℃, be 2: 1 the oxygen and the mist of nitrogen toward the excessive far away volume ratio of the interior feeding of high temperature furnace then, and 740 ℃ of following sintering 10 hours, then with the porous stainless steel helix tube in 15 minutes with-44 ℃/minute speed quenching to 80 ℃, the interior tube-surface of porous stainless steel helix tube and outside tube-surface all to form thickness be that 12 microns oxide layer is as middle barrier layer.
Two ports that will be formed with the porous stainless steel helix tube of oxide layer are sealed up, and send into the rf magnetron sputtering instrument as base material, carry out two target magnetic control sputterings of Pd, Cu.It is the Cu of 99.99%Pd and 99.99% that target is selected purity for use, and the distance between target and the base material remains on 10 centimetres, and base material temperature is set at 450 ℃, and base material rotates with 15 rev/mins speed at pedestal.Back of the body end vacuum is 10 * 10
-5Handkerchief, sputtering pressure are 0.6 handkerchief, and sputtering atmosphere is 99.999% argon gas, are 125 watts to the sputtering power of Pd, are 100 watts to the sputtering power of Cu.Through 2 hours sputter, obtain thickness at last and be 3.5 microns palladium-silver film, palladium is 70: 30 with the weight ratio of silver in this alloy film.Under argon shield, in 800 ℃ high temperature furnace, cool off after the molten alloyization afterwards, obtain complex film M 2 provided by the invention.
Embodiment 3
This embodiment is used to illustrate hydrogen gas segregator provided by the invention.
As shown in Figure 3, adopt the tubular composite membrane of 5 preparations in embodiment 1 to form the shell and tube hydrogen selective, the shell and tube hydrogen selective is seen through chamber 202 be weldingly fixed on two end plates 206 that are arranged in hydrogen collection chamber 203 through chamber 202.End in hydrogen collection chamber 203 forms rich hydrogen gaseous mixture inlet 201 then, and gas distribution grid 205 is placed in the hydrogen collection chamber 203, and gas distribution grid 205 is near rich hydrogen gaseous mixture inlet 201.The other end in hydrogen collection chamber 203 forms residual gas outlet 205.On the position between two end plates 206 of hydrogen collection chamber 203, form hydrogen outlet 204.Make hydrogen gas segregator Q1 provided by the invention as shown in Figure 3.
Embodiment 4
This embodiment is used to illustrate hydrogen gas segregator provided by the invention.
As shown in Figure 4, adopt the tubular composite membrane of preparation among the embodiment 2 to form the helix tube type hydrogen selective, the helix tube type hydrogen selective is seen through chamber 202 be placed in the hydrogen collection chamber 203 through chamber 202.An end that sees through chamber 202 at the helix tube type hydrogen selective forms rich hydrogen gaseous mixture inlet 201 then, and the other end forms residual gas outlet 205.End in hydrogen collection chamber 203 forms hydrogen outlet 204.Make hydrogen gas segregator Q2 provided by the invention as shown in Figure 4.
Embodiment 5-6
Following example illustrates the performance of hydrogen gas segregator separating hydrogen gas provided by the invention.
With rich hydrogen gaseous mixture (55 volume % hydrogen, 2 volume %CO, 18 volume %CO
2, 25 volume %N
2) feed respectively among the hydrogen gas segregator Q1 and Q2 of embodiment 3 and 4 preparations, when depressing mensuration and just started working, 400 ℃ and 10 normal atmospheres ooze hydrogen speed (molal quantity of the hydrogen that sees through on each second every square metre of composite membrane) and the hydrogen selective ratio of the molal quantity of the nitrogen that sees through (molal quantity of the hydrogen that sees through with), promptly initially ooze hydrogen speed and hydrogen selective, the result is as shown in table 1.
Continuous operation was measured and is oozed hydrogen speed and hydrogen selective, and calculate the reduced rate that oozes hydrogen speed and hydrogen selective respectively according to following formula after 1000 hours under these conditions, and the result is as shown in table 1:
Ooze the reduced rate (%) of hydrogen speed=(initially ooze hydrogen speed-continuous operation oozing hydrogen speed after 1000 hours)/initially ooze hydrogen speed * 100%
The reduced rate of hydrogen selective (%)=(the initial hydrogen selective of hydrogen selective-continuous operation after 1000 hours)/initial hydrogen selective * 100%
Table 1
| The composite membrane numbering | M1 | M2 |
| The hydrogen gas segregator numbering | Q1 | Q2 |
| Initially ooze hydrogen speed (mole/square metre second) | 3.2 | 1.2 |
| Continuous operation was oozed hydrogen speed (mole/square metre second) after 1000 hours | 3.04 | 1.15 |
| Ooze the reduced rate (%) of hydrogen speed | 5％ | 4.2％ |
| Initial hydrogen selective | 8000 | 5000 |
| The hydrogen selective of continuous operation after 1000 hours | 7822 | 4940 |
| The reduced rate of hydrogen selective (%) | 2.2％ | 1.2％ |
From the measurement result shown in the table 1 as can be seen, the composite membrane that is used for separating hydrogen gas of the present invention preparation ooze hydrogen speed and hydrogen selective is all very high, and hydrogen speed is oozed in continuous operation after 1000 hours rate of descent only is 5% and 4.2%, the reduced rate of hydrogen selective also only is 2.2% and 1.2%, after working long hours, the composite membrane that is used for separating hydrogen gas provided by the invention oozes hydrogen speed and hydrogen selective and basic identical when just having started working, illustrate after the composite membrane that is used for separating hydrogen gas provided by the invention works long hours and also do not break, separating hydrogen gas functional.
Claims (13)
1. preparation method who is used for the composite membrane of separating hydrogen gas, the surface that this method is included in the porous material supporting layer forms middle barrier layer, form alloy hydrogen permeation membrane layer on the surface of middle barrier layer then, it is characterized in that, described porous material supporting layer is a metal or metal alloy, and the method for barrier layer is oxidized to metal oxide for the metal or metal alloy with the porous material support layer surface in the middle of forming on the surface of porous material supporting layer.
2. method according to claim 1, wherein, the method that the metal or metal alloy of porous material support layer surface is oxidized to metal oxide comprises the porous material supporting layer is contacted with oxidizing gas that it is the metal oxide of 5-20 micron that the condition of contact and the consumption of oxidizing gas are enough to make the porous material support layer surface to form thickness.
3. method according to claim 2, wherein, the condition of described contact comprise the contact temperature be 300 ℃ to less than the temperature of porous material supporting layer metal or metal alloy fusing point, be 6-12 hour time of contact; The theoretical consumption of the oxidizing gas of the metal oxide that the consumption of oxidizing gas is not less than and makes described metal formation thickness is the 5-20 micron.
4. method according to claim 2, wherein, the porous material supporting layer is a stainless steel material, the condition of described contact comprises that the temperature of contact is 400-900 ℃.
5. method according to claim 3 wherein, with before oxidizing gas contacts, rose to the temperature of porous material supporting layer the temperature of contact with the porous material supporting layer from room temperature in 1-5 hour; With after oxidizing gas contacts, the temperature of the porous material supporting layer of barrier layer is reduced to 50-100 ℃ from the temperature of contact in the middle of in 5-20 minute the surface being formed with the porous material supporting layer.
6. method according to claim 1, wherein, the method that forms alloy hydrogen permeation membrane layer on the surface of middle barrier layer is a magnetron sputtering method, magnetron sputtering method is included under the sputtering condition target as sputter is arrived substrate surface, described target is the metal of component alloy hydrogen permeation membrane layer, and base material is formed with the porous material supporting layer of middle barrier layer for the surface; Described sputtering condition comprises that the distance between target and the base material is 5-20 centimetre, and base material temperature is 300-500 ℃, and the velocity of rotation of base material is 15-25 rev/min, and back of the body end vacuum is 3 * 10
-5To 9 * 10
-5Handkerchief, sputtering pressure are the 0.1-1 handkerchief, and sputtering atmosphere is an inert gas, and sputtering power is 10-200 watt, and sputtering time is 1-5 hour.
7. method according to claim 1, wherein, described porous material supporting layer is a stainless steel material, described middle barrier layer is an iron oxide.
8. method according to claim 1, wherein, composite membrane is a tubulose, the composite membrane of tubulose from inside to outside comprises porous material supporting layer, middle barrier layer and alloy hydrogen permeation membrane layer successively.
9. method according to claim 1, wherein, the average pore diameter of porous material supporting layer is the 0.01-2 micron, and thickness is the 0.1-3.0 millimeter, and porosity is 20-50%.
10. method according to claim 1, wherein, the thickness of middle barrier layer is the 5-20 micron, average pore diameter is the 0.01-0.1 micron.
11. method according to claim 1, wherein, alloy hydrogen permeation membrane layer is palladium-silver, palladium-copper alloy or Polarium; The thickness of alloy hydrogen permeation membrane layer is the 0.5-25 micron.
12. hydrogen gas segregator, this hydrogen gas segregator comprises by the compound film formed hydrogen selective that is used for separating hydrogen gas through chamber (202), hydrogen collection chamber (203), rich hydrogen gaseous mixture inlet (201), hydrogen outlet (204) and residual gas outlet (205), hydrogen selective sees through chamber (202) and is arranged in hydrogen collection chamber (203), rich hydrogen gaseous mixture inlet (201) and residual gas outlet (205) see through chamber (202) with hydrogen selective and are communicated with, hydrogen outlet (204) is communicated with hydrogen collection chamber (203), it is characterized in that the composite membrane that is used for separating hydrogen gas is for to be made by any described method of claim 1-11.
13. hydrogen gas segregator according to claim 12, it is tubulation or helix tube form that hydrogen selective sees through chamber (202).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101642684B (en) * | 2008-08-07 | 2011-11-16 | 大连华海制氢设备有限公司 | Multi-channel metal palladium or palladium alloy composite membrane hydrogen separator |
| FR2938270B1 (en) * | 2008-11-12 | 2013-10-18 | Commissariat Energie Atomique | METAL OR POROUS METAL ALLOY SUBSTRATE, PROCESS FOR PREPARING THE SAME, AND EHT OR SOFC METAL SUPPORT CELLS COMPRISING THE SUBSTRATE |
| FR2971614A1 (en) * | 2011-02-11 | 2012-08-17 | Tn Int | DEVICE FOR TRAPPING FLAMMABLE GASES PRODUCED BY RADIOLYSIS OR THERMOLYSIS IN A CONTAINMENT ENCLOSURE |
| US9272269B2 (en) * | 2012-03-08 | 2016-03-01 | National University Of Singapore | Catalytic hollow fibers |
| CN102963868B (en) * | 2012-11-26 | 2017-01-04 | 南京工业大学 | A kind of hydrogen gas segregator |
| CN103579653B (en) * | 2013-10-29 | 2016-01-20 | 上海合既得动氢机器有限公司 | The instant hydrogen manufacturing electricity generation system of methanol-water and control method thereof |
| US10272381B2 (en) * | 2015-03-18 | 2019-04-30 | Shell Oil Company | Method using carbon monoxide resistant membrane to control H2/CO ratio of synthesis gas feed to fischer-tropsch unit |
| KR102359764B1 (en) * | 2016-06-06 | 2022-02-08 | 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 | Method of Forming a Pd-Au Alloy Layer on a Substrate |
| AT15435U1 (en) * | 2016-06-22 | 2017-08-15 | Plansee Se | diaphragm assembly |
| WO2018004723A1 (en) * | 2016-06-28 | 2018-01-04 | Coors W Grover | Reactor-separator elements |
| US20190015775A1 (en) * | 2017-07-12 | 2019-01-17 | Industrial Technology Research Institute | Membrane and method for filtering gas |
| US10668429B2 (en) | 2017-07-12 | 2020-06-02 | Industrial Technology Research Institute | Gas filtration structure and method for filtering gas |
| CN108939944B (en) * | 2018-06-25 | 2021-05-14 | 华南理工大学 | Non-metal ion doped perovskite type mixed conductor hydrogen permeation membrane and preparation method and application thereof |
| CN111545076B (en) * | 2020-05-11 | 2021-04-09 | 广东石油化工学院 | Electric field stable liquid metal composite film and preparation method and application thereof |
| CN113209838A (en) * | 2021-06-21 | 2021-08-06 | 曾祥燕 | High-temperature metal type composite membrane for hydrogen separation and preparation method thereof |
| CN114870648B (en) * | 2022-05-17 | 2023-07-18 | 华南理工大学 | Mixed conductor hydrogen permeable membrane material and preparation method and application thereof |
| CN115138186A (en) * | 2022-06-29 | 2022-10-04 | 中国石油大学(华东) | Hydrogen separation device with spiral structure membrane module |
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