CN103638821B - Defect mending method of palladium composite membrane - Google Patents
Defect mending method of palladium composite membrane Download PDFInfo
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- CN103638821B CN103638821B CN201310721809.9A CN201310721809A CN103638821B CN 103638821 B CN103638821 B CN 103638821B CN 201310721809 A CN201310721809 A CN 201310721809A CN 103638821 B CN103638821 B CN 103638821B
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Abstract
The invention relates to a defect mending method of a palladium composite membrane. According to the defect mending method, SiO2 is deposited at the defect part of the membrane by gas-phase reaction, so that in-situ mending is directly carried out on the palladium membrane in a component without need of disassembling the component, and a mending scheme is provided for the defects generated in the use process of the membrane. According to the specific technical scheme, the defect mending method comprises the steps that the membrane component is arranged in a high-temperature furnace, a silicon source is introduced into the membrane side of the palladium composite membrane in the component, steam of the silicon source occupies the defect position of the membrane, and then oxidative gas is introduced into the base side of the palladium composite membrane in the component, moves to the defect part under the driving of concentration difference, is in contact with the steam of the silicon source and reacts quickly to produce solid particles which are deposited at the defect part, so that the mending purpose is achieved. The defect mending method has the advantages that the defects generated in the use process of the membrane can be mended, the service life of the membrane can be greatly prolonged, the practicability is wide and the operation is convenient.
Description
Technical field
The present invention relates to a kind of palladium-based composite membrane defect mending method, the defect that more particularly, to film produces in use
Repair, realize directly carrying out in-situ repair to the palladium film in assembly, and assembly need not be dismantled.
Background technology
Palladium-based composite membrane combines the advantage of the unique hydrogen permeability energy of palladium film and the high penetration of porous carrier, Hydrogen Separation with pure
The application of change aspect is increasingly extensive.No matter in which aspect application, the hydrogen permeation selectivity of palladium film is all most important, in theory, intact
The hydrogen selectivity of sunken palladium film is infinity.Defective palladium film, either crackle, the big defect such as cut, or pin hole class
Little defect, all can significantly reduce the hydrogen selectivity of film, when the hydrogen selectivity of film do not reach require when, the life-span of film will terminate,
This becomes the key issue of impact palladio composite membrane application, and the service life extending film is necessary.And be your gold in view of palladium
Belong to, and the cost of matrix, if directly discard to cause huge economic loss, repair palladium film defect prolonging service lifetime of film meaning
Great.
Many factors may affect the consistency of film, such as matrix, the preparation method of film, thickness etc..Even completely fine and close
Palladium film be likely to that new defect occurs after hot operation.For reduce film defect, except take preferred substrate, optimize film preparation, increasing
Outside the methods such as blooming thickness, it is also directly a kind of effective ways to film defect mending.With regard to the repairing of palladium film defect, document existing
A little report, Li Anwu etc. [split scarce repairing in Li Anwu, Xiong Guoxing, r.hughes. dense palladium film, Chinese science, 1999,29
(2): 169-173] reverse osmosiss electroless plating method is proposed, what this seminar invented before this replaces reverse osmosis with dilute reducing agent hydrazine solution
The chemical plating repairing method of agent and pd (oh) thoroughly2Colloid pretreatment and chemical plating repairing method [Hu little Juan, Wei Juan, Huang Yan .pd (oh)2Glue
Body pretreatment and electroless plating method repair composite palladium film. Nanjing University of Technology's journal, 2011,33 (2): 43-48].Yuan Lixiang etc. adopts
With " from bottom to top " method repair palladium film [Yuan Lixiang, Xu Hengyong. " from bottom to top " method repair containing defect palladium film, membrane science and skill
Art .2009,29 (3): 48-51].Palladium film is repaired using said method, hydrogen selectivity is improved, but above-mentioned method for repairing and mending pin
To be the defect that film is formed in preparation process, and the defect that film is produced during life-time service, inapplicable.Because
Palladium film need to be sealed in membrane module realizes its application, and when adopting above method to repair, need to disassemble palladium film, unrealistic,
Complex operation is thereby increases and it is possible to cause extra defect due to artificial origin during operation, inapplicable.Exploitation film produces in use
Defect repairing technique, directly in-situ repair is carried out to the palladium film in assembly, significant.
Content of the invention
The purpose of the present invention: provide a kind of palladium-based composite membrane defect mending method, for palladium film defect, especially with process
The defect of middle generation, directly carries out in-situ repair to the palladium film being sealed in assembly, improves the hydrogen separation purity of film, and extending film makes
Use the life-span.For realizing preferable repair efficiency, the solid that reaction generates need to be made only to be deposited on scarce on the basis of not damaging palladium film
Fall into place, select to deposit sio in fault location2, it is because micropore sio2Generate beneficial to hydrogen separation.The resolving ideas of the present invention are:
Silicon source is passed through the film side of palladium-based composite membrane in assembly, silicon source steam occupies film fault location, subsequently oxidizing gas is passed through assembly
The matrix side of interior palladium-based composite membrane, the concentration official post oxic gas molecule of film both sides spreads to film fault location, connects with silicon source vapour molecule
Touch, react at once and generate solids particles precipitate in fault location, until defect mending finishes.Concrete technical scheme is as follows: will
Palladium membrane component is placed in the high temperature furnace of uniform temperature, and temperature control is in the suitable operating temperature range of palladium film (in hydrogeneous atmosphere
300-500℃；Without nitrogen atmosphere 25-500 DEG C).First silicon source is passed through the film side of palladium-based composite membrane in assembly, then by oxidizing gas
Lead to the matrix side of assembly inner membrance, gas flow is unsuitable excessive, in 10-30ml/min about, both sides all keep normal pressure, film both sides
Concentration official post two gas contact in fault location and react, when film is fine and close, reaction is automatically stopped.After reaction terminates, need
To carry out reduction treatment in hydrogen atmosphere.Silicon source is passed through mode two kinds, and one, silicon source is placed in bubbler, it is heated to one
Constant temperature degree (60-100 DEG C), logical noble gases enter the membrane module (pipe between bubbler and reative cell to carry silicon source steam
Road is heated to mutually synthermal in case steam condenses), two, it is injected directly in assembly with syringe such as syringe.Preferably the latter, reason
One, direct injection silicon source, the silicon source vapor concentration of film side is high, can reduce reaction temperature, control in palladium film suitable long-term work temperature
In the range of degree.Two, first injecting silicon source can preferably control reaction in film fault location, realize controlled gas phase reaction, reach height
Effect is repaired.Because first injection silicon source can make film defect can be washed in the silicon source steam of high concentration, so lead to oxidizing gas again
When, because concentration difference oxic gas spread to film fault location, contact with the silicon source vapour molecule of high concentration in film fault location and occur immediately
Reaction, gas phase reaction controls well and occurs in fault location.This method be suitable for palladium film repairing, operator do not need by palladium film from
Disassemble it is not necessary to find the position of palladium film defect in assembly, when the repair is completed, reaction can terminate automatically.
Beneficial effect:
The present invention deposits sio by controlled gas phase reaction in film fault location2Repair palladium film, it is directly right that its ingenious part is
In assembly, palladium film carries out in-situ repair, need not dismantle assembly, easy to operate, low cost.Respectively from the both sides of film lead to reaction raw materials,
This 3 points of concentration difference being preferentially passed through silicon source steam with film both sides makes reaction control well in film fault location, realizes efficient repairing
Mend.The sio of deposition2Not only the effect of filling up is played to film, micropore sio can also be utilized2Hydrogen separating property, be the hydrogen permeability of film
Can contribute.
Brief description
Fig. 1 schematic diagram repairing palladium-based composite membrane defect method disclosed by the invention.
After Fig. 2 adopts this patent methods described to repair palladium film, pd/al2o3The surface topography of composite membrane.
Specific embodiment
Embodiment 1
(1) pd/al in assembly will be sealed in2o3Composite membrane, first carries out flux and hydrogen permeation selectivity test, test result
For: when 350 DEG C, nitrogen flux is 0.086m3h-1m-2bar-1, hydrogen is 9.56m3h-1m-2bar-1, hydrogen nitrogen selectivity is about
111.
(2) assembly is placed in high temperature furnace, and nitrogen purging is warming up to 350 DEG C.
(3) teos is placed in bubbler, temperature control, at 60 DEG C, uses n2Purging, by needle valve and spinner flowmeter
Control purge rates are 20ml/min, are passed through film side, another reaction gas o2It is passed through matrix side, gas flow rate is 15ml/min.
(4) after reaction 6h, then flux and selectivity test are carried out, result is: when 350 DEG C, nitrogen flux is 0.012m3h- 1m-2bar-1, hydrogen is 7.98m3h-1m-2bar-1, hydrogen nitrogen selectivity is about 665, and selectivity improves.
Embodiment 2
(1) pd/al in assembly will be sealed in2o3Composite membrane, first carries out flux and hydrogen permeation selectivity test, test result
For: when 350 DEG C, nitrogen flux is 0.056m3h-1m-2bar-1, hydrogen is 10.23m3h-1m-2bar-1, hydrogen nitrogen selectivity is about
For 183.
(2) assembly is placed in high temperature furnace, and temperature control is at 330 DEG C.
(3) film side in assembly for the needle cylinder injection teos, another reaction gas o are used2It is passed through matrix side, gas flow rate is
15ml/min.
(4) after reaction 4h, then flux and selectivity test are carried out, result is: when 350 DEG C, nitrogen flux is 0.0096m3h-1m-2bar-1, hydrogen is 9.71m3h-1m-2bar-1, hydrogen nitrogen selectivity is about 1012, and selectivity improves nearly an order of magnitude.
Embodiment 3
(1) by the palladium/rustless steel composite membrane being sealed in assembly, flux and hydrogen permeation selectivity test, test knot are first carried out
Fruit is: when 350 DEG C, nitrogen flux is 0.097m3h-1m-2bar-1, hydrogen is 19.86m3h-1m-2bar-1, hydrogen nitrogen selectivity
It is about 204.
(2) assembly is placed in high temperature furnace, and temperature control is at 400 DEG C.
(3) teos is placed in bubbler, temperature control, at 80 DEG C, uses n2Purging, by needle valve and spinner flowmeter
Control purge rates are 20ml/min, are passed through film side, another reaction gas is passed through matrix side, and gas flow rate is 20ml/min.
(4) after reaction 6h, then flux and selectivity test are carried out, result is: when 350 DEG C, nitrogen flux is 0.016m3h- 1m-2bar-1, hydrogen is 16.25m3h-1m-2bar-1, hydrogen nitrogen selectivity is about 1015, and film selectivity improves.
Claims (7)
1. a kind of palladium-based composite membrane defect mending method, it is characterised in that being placed in palladium membrane component in high temperature furnace, silicon source steam is led to
Enter the film side of palladium-based composite membrane in assembly, silicon source steam occupies film fault location, then is passed through oxygen to the matrix side of palladium-based composite membrane in assembly
The property changed gas, oxidizing gas to fault location movement, and are contacted with the silicon source steam of fault location, quickly under the ordering about of concentration difference
Reaction generates sio2It is deposited on fault location, reaches the purpose of repairing, realize the defect direct in-situ of palladium film in assembly is repaired.
2. palladium-based composite membrane defect mending method according to claim 1 is it is characterised in that silicon source steam is to meet gas phase
The siliceous thing of deposition, described siliceous thing is teos or sih4.
3. palladium-based composite membrane defect mending method according to claim 1 is it is characterised in that silicon source steam is passed through the side of assembly
Formula has carrier gas purge or direct injection.
4. palladium-based composite membrane defect mending method according to claim 3 is it is characterised in that carrier gas is noble gases n2, ar or
he.
5. palladium-based composite membrane defect mending method according to claim 1 is it is characterised in that oxidizing gas are o2, h2O or
o3.
6. palladium-based composite membrane defect mending method according to claim 1 it is characterised in that reaction temperature be 300-500 DEG C,
Response time is 2-10h.
7. palladium-based composite membrane defect mending method according to claim 1 is it is characterised in that the film material of palladium-based composite membrane is
Simple metal palladium or palldium alloy, described palldium alloy is palladium-silver, the alloy composite film of porpezite, palladium copper or palladium nickel；The matrix of palladium-based composite membrane
Material is porous ceramicss, cellular glass or porous stainless steel.
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| JP2019521055A (en) | 2016-04-14 | 2019-07-25 | ロッキード・マーチン・コーポレーション | Selective interface relaxation of graphene defects |
| CN109722632A (en) * | 2017-10-31 | 2019-05-07 | 陕西南水汽车配件制造有限公司 | A kind of aluminum alloy control arm forging coarse grains on surface ring control method |
| WO2019132051A1 (en) * | 2017-12-26 | 2019-07-04 | 예일 유니버시티 | Method for restoring damaged water treatment separation membrane by using surface-functionalized silica microparticles |
| CN112546870B (en) * | 2020-11-25 | 2022-09-20 | 南京工业大学 | In-situ repair technology |
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| US5672388A (en) * | 1994-07-08 | 1997-09-30 | Exxon Research & Engineering Company | Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition |
| CN101560654A (en) * | 2008-04-18 | 2009-10-21 | 中国科学院大连化学物理研究所 | Method for repairing defects of palladium and palladium alloy composite membranes |
| CN102491271A (en) * | 2011-12-09 | 2012-06-13 | 丹阳奥恩能源科技发展有限公司 | Method for repairing defects of palladium membrane component |
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Effective date of registration: 20180410 Address after: Zhejiang city of Yiwu Province Yang Cun Lu 322000 No. 288 standard factory building 5 layer A Patentee after: Yiwu wins the new Mstar Technology Ltd Address before: 210009 Gulou District, Jiangsu, Nanjing new model road, No. 5 Patentee before: Nanjing University of Technology |