CN1929900A - Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations - Google Patents
Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations Download PDFInfo
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- CN1929900A CN1929900A CN200580007843.3A CN200580007843A CN1929900A CN 1929900 A CN1929900 A CN 1929900A CN 200580007843 A CN200580007843 A CN 200580007843A CN 1929900 A CN1929900 A CN 1929900A
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Abstract
The present invention relates to a metal palladium composite membrane or an alloy palladium composite membrane in which essentially the metal palladium membrane or alloy palladium membrane exists substantially on the outer surface of the porous substrate support, with little or no presence in the pore channels of the support, and to process for its preparation. The process comprises the steps of treating the porous substrate with a pore filler before plating it with a palladium solution to form the composite membrane.
Description
The present invention relates to a kind of Metal Palladium or alloy palladium composite membrane, it has high saturating hydrogen amount and high separating or the purified hydrogen selectivity.The invention further relates to a kind of preparation method who is used to prepare these described metal or alloy palladium-based composite membranes.
(for example petroleum refining, petrochemical industry and semiconductor machining) and in the growth of the relevant application of new forms of energy (clean fuel that for example is used for fuel cell and vehicle) to the needs of hydrogen in recent years in a lot of fields causes people to separating from admixture of gas and the method for purified hydrogen has produced very high interest.
Palladium film or alloy palladium film are to a great extent because their mismatch current potential makes its membrane reactor that can be used as the selective membrane of separation or purified hydrogen and be used for the hydrogenation/dehydrogenation reaction, so become the theme of many researchs.But these are discovered, owing to saturating hydrogen amount measured in all these researchs is all still extremely low, so must improve the permeability of hydrogen in pure and mild composite membrane.
Another major issue in film research is that below 275 ℃, pure palladium film is owing to the hydrogen that is absorbed is easy to break in phase transition process.This phenomenon is commonly called ' hydrogen embrittlement '.Even knownly at room temperature also can significantly reduce hydrogen embrittlement by forming alloy palladium film such as Pd-Ag alloy film, Pd-Cu alloy film or Pd-Au alloy film.
Film both can pure film form exist also can composite membrane form exist.Pure palladium film, promptly carrier-free palladium film is well known in known field.For guaranteeing that having enough mechanical strengths supports reaction, the respective thickness of film must be greater than 200 microns; Therefore, this regulation thickness has caused low saturating hydrogen amount and very high production cost.So preferred composite films, it is the supported palladium film, wherein the palladium rete links to each other with the porous substrate carrier, thus the required thickness that has reduced the palladium rete thus when keeping whole film mechanical strength has also reduced cost and has improved saturating hydrogen amount.
As shown in prior art, traditional composite membrane is present in the layer of three regulations; Palladium/palldium alloy rete, surface substrate carrier and interconnect the intermediate layer of above-mentioned two layers.Really, in the prior art, for obtain thin palladium/palldium alloy rete on porous substrate, introduced the intermediate layer usually, this makes and has produced three layers composite membrane.Yet still there are the low serious problems of hydrogen amount in this three-decker.
The present invention is absorbed in the low and high problem of production cost of above-mentioned hydrogen amount, has proposed directly to form palladium-based composite membrane on the porous substrate carrier surface and do not use the technology in intermediate layer between film and carrier.This technology is different from generation the double-layered compound film of three layers of traditional composite membrane.
The present invention is absorbed in simply, easy operating pass through occupy hole path or substrate surface defective in advance and come method the porous substrate modification.Just can use the thin dense palladium film of chemically plating Preparation Method preparation thus.
In the known preparation method of three layers of traditional palladium/palladium alloy composite membrane, comprise such method, wherein at first to the porous substrate carrier carry out ' finishing ', with overcome with the surface on have the macropore problem relevant with defective.These described defectives are to be produced by the inhomogeneities of the distribution of pores of carrier surface and carrier, and thereby make and be difficult to form the dense palladium film at carrier surface that this has reduced the hydrogen permeation selectivity of film again.Incrustation is used for eliminating the existence of macropore and defective, and can carry out by following arbitrary method:
A) use porous surface modifier such as γ-Al
2O
3, by applying or cast in the substrate surface coating film to generate the intermediate layer.
B) use the porous material of aperture, as γ-Al less than the substrate carrier hole path
2O
3, ZrO
2, SiO
2Or CeO
2, insert in the big hole path or defective of substrate surface.
But, there are some serious problems in these two kinds traditional ' finishing ' methods.For above-mentioned first kind ' finishing ' method, porous material such as γ-Al
2O
3Be used on the passage of substrate surface by applying or the thin intermediate layer of casting coating.Unfortunately palladium plating solution can enter described hole path when film forms, and causes palladium to be deposited in the passage of base material, has produced second resistance that hydrogen is permeated thus effectively and has reduced saturating hydrogen amount.
In described second trailing, the aperture is less than the porous material of substrate carrier hole path, as γ-Al
2O
3, ZrO
2, SiO
2Or CeO
2, be used to before chemical plating, insert in the big hole path or defective of substrate surface.For the reason identical with first method, the method also has problems.Chemical plating fluid enters the hole path of selected base material inevitably.Thus, the porous material of inserting the base material hole path will constitute not only second resistance of hydrogen infiltration and saturating thus hydrogen amount but also quite low.
Therefore the object of the present invention is to provide the porous substrate carrier is carried out the new method that active surface is modified, have the double-deck palladium or the palladium alloy composite membrane of high saturating hydrogen amount with preparation.
For achieving the above object, the present invention mainly is the double-level-metal palladium-based composite membrane that is made of porous substrate carrier and palladium film.This metal palladium-based composite membrane is characterised in that palladium metal is present in basically on the outer surface of porous substrate carrier and exists hardly or be not present in the hole path of base material.
The present invention also comprises the double-deck palladium alloy composite membrane that is made of porous substrate carrier and palladium alloy membrane.This palladium alloy composite membrane is characterised in that palladium alloy membrane is present in basically on the outer surface of porous substrate carrier and exists hardly or be not present in the hole path of base material.
According to preparation process of the present invention, in the hole path of carrier, ' there is or do not exist ' palladium hardly, because our hole filler occupies the hole path of porous substrate in advance, this has prevented that palladium plating solution from entering base material.
According to a preferred embodiment of the present invention, ' existing or do not exist ' palladium to be defined as the porous substrate carrier in the hole path of carrier hardly contains less than the total palladium that exists in 5% the whole composite membrane heavy, particularly heavy less than the total palladium that exists in 2% the whole composite membrane.
The present invention relates to all can be by above-mentioned two kinds of double-layered compound films of following preparation technology's acquisition.According to a preferred embodiment of the invention, this technology is undertaken by following consecutive steps:
1. use the hydrochloric acid weak solution that the porous substrate carrier is rinsed and wash, washing is used dilute solution of sodium hydroxide to rinse and is washed, then with the distilled water washing, with solvent such as CCl
4Rinse and wash, and dry under environmental condition.
2. the porous substrate carrier that will as above prepare under vacuum condition then soaked 20 minutes in the solution of hole filler.The metering-orifice filler of crossing that remains on the substrate surface is preferably rinsed to wash by machinery and is for example cleaned substrate surface and remove with the distilled water washing then.According to a preferred embodiment of the invention, repeat this method of modifying 5-6 time.
3. after finishing, with the porous substrate carrier respectively at SnCl
2In sensitization and at PdCl
2Activate in the solution.According to a preferred embodiment of the invention, this process repeats 4 times.Because Pd
2+By Sn
2+The Pd that reduces and form
0Atomic adsorption is at substrate surface, and is formed for the nuclear of further palladium growth.
4. porous substrate is immersed in the chemical plating fluid (electroless plating) then, its classical group becomes [Pd (NH
3)
2] Cl
2(4g/l), EDTA2Na (65g/l), NH
2-NH
2H
2O (0.6g/l), NH
3H
2O (28%) (300ml/l), pH=～10,50 ℃.At Pd
0Formation in, the Pd that in chemical plating fluid, exists with metastable state metal complex ion
2+Be reduced the agent hydrazine and be reduced into Pd continuously
0Pd nuclear becomes the big dense palladium film that forms gradually.
5. then porous substrate is carried out post processing, the hole filler that wherein is positioned at the porous substrate hole path is removed or reduced volume by heating or physical/chemical dissolving.Then with the Pd film 200 ℃ in nitrogen dry 60 minutes, afterwards again 500 ℃ of calcination 120 minutes.
Fig. 1 is illustrating of described preparation process operation and formed film.Four corresponding preparation processes are as follows:
(1) modification of base material modification-porous carrier comprises with hole filler (Al (OH) for example
3) occupying the passage of porous substrate in advance, wherein said hole filler can be removed or part is removed by post processing.
(2) the palladium karyomorphism becomes-examines by sensitization and activating technology formation palladium.
(3) film forms-passes through the method formation palladium or the palladium alloy membrane of chemical plating.
(4) modifier decomposition-described hole filler (Al (OH) for example
3) be broken down into porous Al
2O
3, it will keep constituting H
2The base material passage that permeates free path is open-minded.
As indicated above, the hole filler is the material with following character:
Can in the modification technique step, occupy the passage of porous substrate and the defective of substrate surface randomly in advance, and
Prevent that palladium from entering in the hole in preparation process.
Preferably, described hole filler is subsequently by by post processing, and for example heat treatment (preferably thermal decomposition) and/or physical dissolution are removed or part is removed.
Described hole filler can be preferably gel colloidal sol, colloid or precipitation.
They preferably are selected from Al colloidal sol, Si colloidal sol, Ti colloidal sol, Zr colloidal sol and/or Ce colloidal sol.They also can preferably be selected from hydroxide colloid, alkali carbonate colloid and/or carbonate colloid.
They also can preferably be selected from precipitation of hydroxide, alkali carbonate precipitation and/or carbonate deposition.
Most preferably, used hole filler is characterised in that particle diameter less than 0.2 micron according to the present invention, preferably less than 0.1 micron, most preferably less than 0.05 micron.
In technical scheme of the present invention, those can processed (for example thermal decomposition) become as the chemical particle of hole filler small porous particle or by thermal decomposition process will significantly dwindle the chemical particle of its volume such as gel, colloidal sol, colloid, precipitation (Al colloidal sol, Si colloidal sol, Ti colloidal sol, hydroxide colloid, alkali carbonate colloid, carbonate deposition etc.) is taken as the hole filler.Under the vacuum condition, the porous substrate film is suspended in colloidal sol, colloid or the precipitation solution of described hole filler, and the hole path that the particulate of hole filler enters porous substrate is particularly in major path or the defective, the formation that this will modify substrate surface and will be of value to the dense palladium film.Because the thermal decomposition process after the palladium film forms is dwindled the hole packing volume or resolved into porous material, for seeing through film, hydrogen provides free path, so the metal palladium-based composite membrane that is obtained by modified porous base material will have high saturating hydrogen amount.
According to a preferred embodiment of the invention, the material as the porous substrate carrier of metal palladium-based composite membrane or alloy palladium composite membrane is selected from following porous material: porous stainless steel, nickel porous, cellular glass or porous ceramics.According to a preferred embodiment of the invention, the preferred material as carrier is porous stainless steel and porous ceramics.
Feature of the present invention is as follows:
I. technology is simple.In the present invention, vacuum is the unique conditional that the hole filler enters the porous substrate hole path.Operation and technology are all very simple.
Ii. be widely used.The base material film that the present invention is not limited in Metal Palladium/alloy palladium composite membrane preparation is modified; It also can be applicable to the modification of any porous substrate of other metal film.But, the hole filler be those not with the filler of plating bath reaction.
Iii. production cost is low.In the present invention, used the cheap hole filler that will decompose by thermal decomposition, as colloidal sol, colloid or precipitation.Used raw material are cheap, technology of preparing is simple, so the production cost of technology is low.
Embodiment
In following examples, details of the present invention will be described.In following examples, saturating hydrogen amount and permselective property are all measured down at 500 ℃.
Embodiment 1
Colloid for preparing: under 55 ℃, pH=8, in beaker, drip aluminum nitrate solution and sodium carbonate liquor simultaneously to obtain alkali alumina carbonate colloid.Colloid is washed 6 times with distilled water.If replace above-mentioned sodium carbonate liquor as precipitating reagent with potash, ammonia, NaOH and/or potassium hydroxide solution, then will obtain corresponding colloid or precipitation.
The porous substrate finishing: base material is the alumina porous ceramic pipe.At first porous substrate is rinsed and washed, with the distilled water washing, use CCl more then with dilute hydrochloric acid solution and diluted sodium hydroxide solution
4Rinse and wash, dry then.To rinse the alumina porous ceramic pipe of washing and immerse above-mentioned colloidal solution under vacuum condition, colloidal solid will enter the hole path and the blemish of alumina porous ceramic pipe.Remove the excessive surface holes filler that remains on the carrier surface by mechanical chipping then.
The palladium-based composite membrane preparation: the porous substrate after will modifying is respectively at SnCl
2Solution sensitization and PdCl
2Activate in the solution.Above-mentioned steps repeats 4 times.Because Pd
2+By Sn
2+The Pd that reduces and form
0Atomic adsorption is to substrate surface.
Porous substrate is immersed in the chemical plating fluid, and its classical group becomes [Pd (NH
3)
2] Cl
2(4g/l), EDTA2Na (65g/l), NH
2-NH
2H
2O (0.6g/l), NH
3H
2O (28%) (300ml/l), pH=10,50 ℃.In the catalysis of Pd nuclear, the pd that in chemical plating fluid, exists with metastable metal complex ion
2+Be reduced the agent hydrazine and be reduced into Pd continuously
0Pd
0Become gradually enough greatly to form the dense palladium film.
Post processing: palladium-based composite membrane stands drying and at 500 ℃ of alkali alumina carbonate colloid hole fillers that stand in calcination is present in porous substrate with decomposition the hole path at 200 ℃ subsequently.
Table 1 has provided the (NO with Al
3)
3The porous alumina ceramic pipe is carried out the saturating hydrogen performance of the prepared palladium-based composite membrane of modification with different precipitating reagents.
The saturating hydrogen performance of table 1 metal palladium-based composite membrane
| Precipitating reagent | Saturating hydrogen amount m 3·m -2·h -1·bar -1 | Hydrogen selectivity H 2/N 2 |
| Na 2CO 3 K 2CO 3 NH 3·H 2O NaOH KOH | 74 69 67 56 70 | 8800 5800 7200 4200 5900 |
Embodiment 2
Colloid for preparing: with identical among the embodiment 1.
The porous substrate finishing: base material is a porous stainless steel.Identical among method of modifying and the embodiment 1.Identical among post-processing approach and the embodiment 1.
Table 2 has provided the (NO with Al
3)
3Porous stainless steel is carried out the saturating hydrogen performance of the prepared palladium-based composite membrane of modification with different precipitating reagents.
The saturating hydrogen performance of table 2 metal palladium-based composite membrane
| Precipitating reagent | Saturating hydrogen amount m 3·m -2·h -1·bar -1 | Hydrogen selectivity H 2/N 2 |
| Na 2CO 3 K 2CO 3 NH 3·H 2O NaOH KOH | 38 34 29 33 34 | 4400 5100 3500 3900 4100 |
Embodiment 3
Colloid for preparing: under 55 ℃, pH=9, in a beaker, drip cerous nitrate solution and sodium carbonate liquor simultaneously to obtain alkaline carbonic acid cerium colloid.Colloid is washed 5 times with distilled water.If replace above-mentioned sodium carbonate liquor as precipitating reagent with potash, ammonia, NaOH and/or potassium hydroxide solution, then will obtain corresponding colloid or precipitation.
The porous substrate finishing: base material is the alumina porous ceramic pipe.At first porous substrate is rinsed and washed, with the distilled water washing, use CCl more then with dilute hydrochloric acid solution and diluted sodium hydroxide solution
4Rinse and wash, dry then.To rinse the alumina porous ceramic pipe of washing and immerse above-mentioned colloidal solution under vacuum condition, colloidal solid will enter the hole path and the blemish of alumina porous ceramic pipe.Remove the excessive surface holes filler that remains on the carrier surface by mechanical chipping then.
Palladium-based composite membrane preparation: identical among operation and the embodiment 1.
Identical among post-processing approach and the embodiment 1.
Table 3 has provided the (NO with Ce
3)
3The porous alumina ceramic pipe is carried out the saturating hydrogen performance of the prepared palladium-based composite membrane of modification with different precipitating reagents.
The saturating hydrogen performance of table 3 metal palladium-based composite membrane
| Precipitating reagent | Saturating hydrogen amount m 3·m -2·h -1·bar -1 | Hydrogen selectivity H 2/N 2 |
| Na 2CO 3 K 2CO 3 NH 3·H 2O NaOH KOH | 72 70 69 62 56 | 7600 4800 6200 3100 4100 |
Embodiment 4
Colloid for preparing: CO
2Inject Ca (OH)
2In the solution to form CaCO
3Precipitation will precipitate to rinse with distilled water and wash 5 times.
The porous substrate finishing: base material is the alumina porous ceramic pipe.At first porous substrate is rinsed and washed, with the distilled water washing, use CCl more then with dilute hydrochloric acid solution and diluted sodium hydroxide solution
4Rinse and wash, dry then.Under vacuum condition, will rinse the alumina porous ceramic pipe of washing and immerse above-mentioned CaCO
3In the precipitation suspension, CaCO
3Deposit seed will enter the hole path and the blemish of alumina porous ceramic pipe.Remove the excessive surface holes filler that remains on the carrier surface by mechanical chipping then.
Palladium-based composite membrane preparation: identical among operation and the embodiment 1.
Identical among post-processing approach and the embodiment 1.
By chemical plating method with use CaCO
3Precipitation is carried out the prepared palladium-based composite membrane of modification to the porous alumina ceramic base material and is shown 66m
3M
-2H
-1Bar
-1Saturating hydrogen amount and 3800 hydrogen permeation selectivity (H
2/ N
2).
Embodiment 5
The porous substrate finishing: will be used as the surface holes filler by γ-AlOOH colloidal sol that the SB powder obtains, base material is the alumina porous ceramic pipe.At first porous substrate is rinsed and washed, with the distilled water washing, use CCl more then with dilute hydrochloric acid solution and diluted sodium hydroxide solution
4Rinse and wash, dry then.To rinse the alumina porous ceramic pipe of washing and immerse above-mentioned Al sol solution under vacuum condition, the AlOOH particle will enter the hole path and the blemish of alumina porous ceramic pipe under vacuum condition.Remove the excessive surface holes filler that remains on the carrier surface by mechanical chipping then.
Palladium-based composite membrane preparation: identical among operation and the embodiment 1.
Identical among post-processing approach and the embodiment 1.
By chemical plating method with γ-AlOOH colloidal sol the porous alumina ceramic base material is carried out the prepared palladium-based composite membrane demonstration 58m of modification
3M
-2H
-1Bar
-1Saturating hydrogen amount and 3800 hydrogen permeation selectivity (H
2/ N
2).
Embodiment 6
Colloid for preparing: identical among operation and the embodiment 3.Porous substrate finishing: identical among operation and the embodiment 3.Palladium-silver composite membrane preparation: initial, identical among operation and the embodiment 1.Then, the palladium-based composite membrane that obtains is immersed in the chemical plating fluid of argentiferous, wherein the composition of chemical plating fluid is AgNO
3(9g/l), natrium citricum (6.5g/l), formaldehyde (37wt%) (18ml/l), cushioning liquid (PH=10) is (90ml/l).Under 450 ℃, will form the Pd-Ag alloy film after the composite membrane calcination 4h that be obtained.
Identical among post-processing approach and the embodiment 1.
Table 6 has been listed the (NO with Ce
3)
3The porous alumina ceramic pipe is carried out the saturating hydrogen performance of the prepared palladium-silver composite membrane of modification with different precipitating reagents.
The saturating hydrogen performance of table 6 Pd-Ag alloy composite film
| Precipitating reagent | Saturating hydrogen amount M 3·m -2·h -1·bar -1 | Hydrogen selectivity H 2/N 2 |
| Na 2CO 3 K 2CO 3 NH 3·H 2O NaOH KOH | 72 62 53 51 54 | 6900 5200 4800 5800 6200 |
Embodiment 7 (being used for contrast)
Porous substrate finishing: with porous gamma-Al
2O
3Be suspended in the distilled water, base material is the alumina porous ceramic pipe.Under vacuum condition, the Woelm Alumina porous ceramic pipe is immersed in the above-mentioned suspension porous gamma-Al
2O
3Particle will enter the hole path and the blemish of alumina porous ceramic pipe under vacuum condition.So base material is modified.The same CeO that uses
2, TiO
2And ZrO
2Replace γ-Al
2O
3Carry out finishing.
Palladium-based composite membrane preparation: identical among operation and the embodiment 1.
Table 7 has been listed with different hole filler (γ-Al
2O, CeO
2, TiO
2, ZrO
2) the porous alumina ceramic pipe carried out the saturating hydrogen performance of the prepared palladium-based composite membrane of modification.
The saturating hydrogen performance of table 7 composite palladium film
| The hole filler | Saturating hydrogen amount M 3·m -2·h -1·bar -1 | Hydrogen selectivity H 2/N 2 |
| γ-Al 2O 3 CeO 2 TiO 2 ZrO 2 | 12.8 14.4 13.7 10.8 | 2300 1800 1900 2400 |
As can be seen from Table 7, use traditional γ-Al
2O
3, CeO
2, TiO
2, ZrO
2The porous alumina ceramic tube-surface is carried out modification will cause that palladium is deposited on γ-Al when film forms
2O
3, CeO
2, TiO
2, ZrO
2Passage in, and further cause the saturating hydrogen amount of the palladium-based composite membrane that obtained to reduce.
Embodiment 8 (being used for contrast)
The porous substrate finishing: base material is a porous stainless steel.Surface modification method is with identical shown in the embodiment 7.
Palladium-based composite membrane preparation: identical among step and the embodiment 1.
Table 8 has been listed with different hole filler (γ-Al
2O
3, CeO
2, TiO
2, ZrO
2) porous stainless steel carried out the saturating hydrogen performance of the prepared palladium-based composite membrane of modification.
The saturating hydrogen performance of table 8 composite palladium film
| The hole filler | Saturating hydrogen amount M 3·m -2·h -1·bar -1 | Hydrogen selectivity H 2/N 2 |
| γ-Al 2O 3 CeO 2 TiO 2 ZrO 2 | 6.2 9.8 3.2 5.1 | *3100 3200 2200 1800 |
As can be seen from Table 8, use traditional γ-Al
2O
3, CeO
2, TiO
2, ZrO
2The porous stainless steel tube-surface is carried out modification will cause that palladium is deposited on γ-Al when film forms
2O
3, CeO
2, TiO
2, ZrO
2Passage in, and further cause the saturating hydrogen amount of the palladium-based composite membrane that obtained to reduce.
Claims (16)
1. a double-level-metal palladium or palladium alloy composite membrane that is made of porous substrate carrier and palladium or palladium alloy membrane is characterised in that palladium metal is present in basically on the outer surface of porous substrate carrier and exists hardly or be not present in the hole path of base material.
2. one kind prepares the double-level-metal palladium that is made of porous substrate carrier and palladium or palladium alloy membrane or the method for palladium alloy composite membrane, is characterised in that following consecutive steps:
1) flushing/washing and dry porous substrate carrier,
2) handle the porous substrate carrier with the hole of modifying carrier and the defective of randomly modifying substrate surface with the hole filler,
3) randomly, when there was excessive hole filler in the substrate carrier surface, the cleaned base material carrier to be removing these excessive surface holes fillers,
4) with sensitization of palladium solution and the substrate carrier that activates modified,
5) with palladium solution resulting carrier is carried out plating with the formation double-layered compound film,
6) drying and
7) randomly, the composite membrane of gained is carried out post processing, wherein will remain in hole filler in the porous substrate hole path and remove or dwindle its volume by heating or physical/chemical dissolving.
3. according to the method for claim 2, be characterised in that step 2 is under vacuum, preferably by carrying out in the solution that porous substrate is immersed in the hole filler, occupied in advance by filler and in ensuing preparation process, do not have palladium to enter in the hole with the hole that guarantees base material and the defective that randomly guarantees base material.
4. according to the method for claim 2 or 3, be characterised in that in step 4 the porous substrate carrier is by respectively at SnCl
2Sensitization and at PdCl in the solution
2Activate in the solution.
5. according to any one method among the claim 2-4, be characterised in that porous substrate is dipped in the chemical plating fluid in step 5.
6. according to the method for claim 5, wherein the classical group of chemical plating fluid becomes [Pd (NH
3)
2] Cl
2, EDTA2Na, NH
2-NH
2H
2O, NH
3H
2O.
7. according to any one method among the claim 2-6, be characterised in that post-processing step 7 is enforceable.
8. according to the method for claim 7, wherein composite membrane is dried then at least 300 ℃ of calcination.
9. according to any one method among the claim 2-8, be characterised in that used hole packing material size less than 0.2 micron, preferably less than 0.1 micron, most preferably less than 0.05 micron.
10. according to any one method among the claim 2-9, be characterised in that the surface holes filler is selected from gel, colloidal sol, colloid or precipitation.
11. according to the method for claim 10, its mesopore filler is selected from Al colloidal sol, Si colloidal sol, Ti colloidal sol, Zr colloidal sol and/or Ce colloidal sol.
12. according to the method for claim 10, its mesopore filler is selected from
13. hydroxide colloid, alkali carbonate colloid and/or carbonate colloid.
14. according to the method for claim 10, its mesopore filler is selected from precipitation of hydroxide, alkali carbonate precipitation and/or carbonate deposition.
15. one kind can be by the double-level-metal palladium or the palladium alloy composite membrane of the method acquisition of any one among the claim 2-13.
16., be characterised in that the porous substrate carrier is selected from one of following porous material: porous stainless steel, nickel porous, cellular glass or porous ceramics according to the composite membrane of claim 1 or 14 or according to any one preparation method among the claim 2-13.
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|---|---|---|---|
| CN200580007843.3A CN1929900A (en) | 2004-01-09 | 2005-01-07 | Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations |
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|---|---|---|---|
| CN200410021025.6 | 2004-01-09 | ||
| CNB2004100210256A CN1327942C (en) | 2004-01-09 | 2004-01-09 | Composite metal palladium membrane or alloy palladium membrane and its preparing method |
| PCT/GB2005/000041 WO2005065806A1 (en) | 2004-01-09 | 2005-01-07 | A metal palladium composite membrane or alloy palladium composite membrane and their preparation methods |
| CN200580007843.3A CN1929900A (en) | 2004-01-09 | 2005-01-07 | Metallic palladium composite membrane or alloy palladium composite membrane and method for their preparations |
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| CN104023831A (en) * | 2012-01-10 | 2014-09-03 | 韩国能源技术研究院 | Heat resistant hydrogen membrane and manufacturing method thereof |
| CN107376661A (en) * | 2017-08-31 | 2017-11-24 | 廊坊师范学院 | A kind of preparation method of palladium base composite membrane |
| CN108144460A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | The preparation method and applications of palladium-ceramics-palladium two-layer compound membrane material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103118772A (en) * | 2010-08-13 | 2013-05-22 | Sk新技术株式会社 | Pore-protected multi-layered composite separator and the method for manufacturing the same |
| CN103118772B (en) * | 2010-08-13 | 2015-04-01 | Sk新技术株式会社 | Pore-protected multi-layered composite separator and the method for manufacturing the same |
| CN103157389A (en) * | 2011-12-14 | 2013-06-19 | 南京髙谦功能材料科技有限公司 | Method for preparing asymmetric porous metal film |
| CN103157389B (en) * | 2011-12-14 | 2016-03-02 | 南京髙谦功能材料科技有限公司 | A kind of preparation method of asymmetric porous metal film |
| CN104023831A (en) * | 2012-01-10 | 2014-09-03 | 韩国能源技术研究院 | Heat resistant hydrogen membrane and manufacturing method thereof |
| CN108144460A (en) * | 2016-12-05 | 2018-06-12 | 中国科学院大连化学物理研究所 | The preparation method and applications of palladium-ceramics-palladium two-layer compound membrane material |
| CN107376661A (en) * | 2017-08-31 | 2017-11-24 | 廊坊师范学院 | A kind of preparation method of palladium base composite membrane |
| CN107376661B (en) * | 2017-08-31 | 2020-08-18 | 廊坊师范学院 | Preparation method of palladium-based composite membrane |
| CN111111463A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院大连化学物理研究所 | Finger-type palladium-based composite membrane with gap structure and preparation and application thereof |
| CN111111463B (en) * | 2018-11-01 | 2021-09-28 | 中国科学院大连化学物理研究所 | Finger-type palladium-based composite membrane with gap structure and preparation and application thereof |
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