CN100563801C - A kind of preparation method of multi-channel type hydrogen permeation palladium-based composite membrane - Google Patents
A kind of preparation method of multi-channel type hydrogen permeation palladium-based composite membrane Download PDFInfo
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- CN100563801C CN100563801C CNB2007101309050A CN200710130905A CN100563801C CN 100563801 C CN100563801 C CN 100563801C CN B2007101309050 A CNB2007101309050 A CN B2007101309050A CN 200710130905 A CN200710130905 A CN 200710130905A CN 100563801 C CN100563801 C CN 100563801C
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Abstract
The present invention relates to a kind of efficient hydrogen permeation membrane that is used for Hydrogen Separation and purifying---the chemically plating Preparation Method of multi-channel type palladium-based composite membrane.Earlier the carrier outside is wrapped up with plastics or elastomeric material, plating bath is placed in the passage of carrier then, and reducing agent is added in the plating bath, plating bath is stirred by the gas Bubbling method.The present invention is simple to operate, has realized the even growth of rete effectively, has guaranteed the compactness and the adhesive force of palladium film.Plated film can at room temperature carry out, and has reduced the discharging of toxic gas.
Description
Technical field:
The present invention relates to a kind of preparation method of multi-channel type palladium-based composite membrane, prepared palladium membrane can provide bigger membrane area, is specially adapted to the hydrogen membrane separator.
Background technology:
Palladium and palladium alloy membrane have good hydrogen penetrating quality, can be used for the separation and the purifying of hydrogen.For example, the palladium-silver membrane filter method technology of producing High Purity Hydrogen has had the history of decades.In recent years research and development mainly concentrate on palladium-based composite membrane, are about to ultra-thin palladium film and are deposited on the porous material to replace traditional self-supporting type palladium film.Can reduce film thickness greatly so on the one hand, save precious metal palladium; On the other hand the permeability of hydrogen is largely increased [Huang Yan, Li Xue, Fan Yiqun, Xu Nanping. the progress of hydrogen permeation palladium-based composite membrane: principle, preparation and sign. chemical progress, 2006,18 (2-3): 230-238].The carrier material of palladium film has a lot, but mainly is porous ceramic pipe and porous stainless steel, wherein is most widely used with the former again, and this mainly gives the credit to its excellent chemical stability and ripe preparation technology.At present, the main application of porous ceramic pipe is a filter core, and it has two kinds of single channel and multichannels, and wherein, the used porous ceramic filter element of large-scale commercial applications filter mainly is a multi-channel type, and this obviously is because its unit volume filter core can provide higher filtering surface.Related palladium film ceramic monolith nearly all is a single channel type in existing document and the patent report, palladium film or be plated in the earthenware outside or be plated in the inboard.Because the membrane area of every single channel type palladium-based composite membrane is limited, though can simply increase membrane area by the quantity that increases the film pipe, this has increased the occupied space of film pipe again, has improved equipment investment and has increased the difficulty of installing and monitoring.Based on above reason, be that the novel palladium film of carrier will have the better application prospect with the multi-channel type porous ceramics, its working method is generally as shown in Figure 1.High pressure mixing gas feeds from an end in duct, and hydrogen sees through the palladium film and obtains pure hydrogen along the effusion of carrier cell walls, and residual gas is discharged from the duct other end.
Because the unit volume of multi-channel type palladium film can provide bigger membrane area, thereby can make hydrogen gas segregator volume when guaranteeing the hydrogen flux more small and exquisite, be particularly useful for portable or hydrogen production plant.In addition, multi-channel type palladium film is interior membranous type, and its super thin metal layer is not easy impaired in install operation process.But the passage of multichannel ceramic monolith has huge draw ratio (being orifice throat length and the ratio of channel diameter), has brought great difficulty for the preparation of palladium film, and therefore, can the preparation of multi-channel type palladium film be its key in application of succeeding.
Preparation technology about the load type palladium film in the document has a lot, as electroless plating method, galvanoplastic, PVD method, CVD method, high speed oxygen flame (HVOF) hot spray process, magnetron sputtering method, plasma spraying method, photocatalytic method or the like, wherein, electroless plating method has been acknowledged as the most successful technology.Its principle is to deposit the layer of metal particulate as catalyst (being surface active) at porous ceramic surface earlier, after immersing plating bath, under the effect of reducing agent, but the reduction of palladium ion and make the Metal Palladium of generation cover the surface of these catalyst particles in these catalyst catalysis plating baths, thereby the Metal Palladium layer that has generated still can continue the above-mentioned reaction of catalysis and cause that the growth of palladium layer thickens, and stops until reaction.Therefore, the chemical plating autocatalytic plating that is otherwise known as.Chemical plating generally comprises four steps such as the preliminary treatment, surface active, chemical plating, post processing of carrier.Method for activating surface has a lot, but the overwhelming majority is at carrier surface plated metal palladium particulate, and that relatively more commonly used is SnCl
2/ PdCl
2Method.Majority has adopted higher chemical plating temperature in the document, can cause the ammoniacal liquor in the plating bath to decompose fast on the one hand, can cause the discharging of ammonia and poisonous hydrazine steam on the other hand, causes environmental pollution; This patent has proposed effective preparation technology at the key issue in the chemical plating preparation of multichannel palladium film.
Cellular ceramic substrate is a multi-channel type, and its passage is carefully grown, and the plated film difficulty is big.The problem that is faced mainly contains: the mass transfer problem of palladium ion and reducing agent causes the thick and intermediate thin of palladium fenestra mouth easily, local reaction is overrun and cause the consequence of palladium precipitation; The a large amount of nitrogen bubble that generate in the course of reaction are attached to the palladium laminar surface, hinder the even growth of palladium layer; Porous carrier has entering of plating bath in its hole wall behind the contact plating bath, and if the gas that produces in the plating bath can not in time discharge, then can bring pressure to the palladium film of channel surface, light then damage the adhesive force of palladium film, heavy then cause the foaming of palladium film even break.
Summary of the invention:
Purpose of the present invention has proposed a kind of with the carrier outer wrap in order to overcome problems such as prior art chemical plating needs higher temperature, the discharging of poisonous hydrazine steam, plated film difficulty are big, plating bath places the preparation method of the bubble type multi-channel type palladium-based composite membrane of carrier passage inboard.
Technical scheme of the present invention is: in the chemical plating process, the eliminating that reaction generates nitrogen can realize that method has mechanical agitation by the strong agitation to plating bath, the pump circulation of plating bath, the rotation of carrier.But, conventional alr mode can't make the plating bath in the elongated passageway obtain stirring, obviously better not as the carrier mixing effect that in axial direction reciprocating motion causes in plating bath, because this can cause plating bath washing away fast the carrier passage, not only guaranteed the homogeneity of bath concentration, the nitrogen bubble that more helps the reacting generation metal surface that speeds away.During chemical plating, with the carrier outer wrap, plating bath places carrier passage inboard, makes plating bath and carrier passage form excellent contact, and plating bath produces certain pressure to the carrier cell walls.
Among the present invention, the reducing agent hydrazine does not mix with palladium complex ion plating bath in advance, but slowly adds in the plating bath with pump.In initial reaction stage, palladium complex ion concentration height in the plating bath, the addition of needs control reducing agent is to prevent the too fast generation palladium precipitation of reaction speed.Along with the carrying out of reaction, palladium complex ion concentration descends, and can suitably accelerate the addition of reducing agent, to keep reaction speed faster.Reaction is last, and the palladium complex ion is consumed totally, can add excessive reducing agent, to guarantee the conversion ratio of palladium.Experiment finds that this method almost can realize 100% palladium conversion ratio, has avoided the waste of precious metal palladium, and the total amount of palladium can be estimated according to the inventory of plating bath in the rete, can further estimate film thickness thus.
Concrete technical scheme of the present invention is:
A kind of preparation method of multi-channel type hydrogen permeation palladium-based composite membrane, concrete steps comprise four steps of preliminary treatment, surface active, chemical plating, post processing of carrier, after it is characterized in that multichannel carrier inner surface activates, earlier the leakage that prevents plating bath is wrapped up with plastics or elastomeric material in the carrier outside, then plating bath is placed in the passage of carrier; Again reducing agent is added in the plating bath; Passing passage by the gas bubbling stirs plating bath.
Wherein said multichannel carrier is the multi-channel type ceramic monolith; The number of active lanes and the shape of multichannel carrier are not limit, the length of carrier and diameter ratio between 1-60, preferred 1-30.
Described gas is nitrogen, compressed air, oxygen or argon gas etc., and the mode of passing passage by bubbling realizes the stirring of plating bath.
Reducing agent is not to add in the plating bath before chemical plating begins among the present invention, but with pump it is added in the plating bath after plating bath adds in the carrier passage.The adding speed of reducing agent is controlled at 0.05-5ml/min.In the commercialization preparation process, in order to save time, the adding speed of reducing agent can be unlike the laboratory constant speed, in initial reaction stage, palladium complex ion concentration height in the plating bath needs the addition of control reducing agent, to prevent the too fast generation palladium precipitation of reaction speed.Along with the carrying out of reaction, palladium complex ion concentration descends, and can suitably accelerate the addition of reducing agent, to keep reaction speed faster.Reaction is last, and the palladium complex ion is consumed totally, can add excessive reducing agent, to guarantee the conversion ratio of palladium.
Described palladium plating solution of the present invention is: with the plating bath cumulative volume is benchmark, Pd
2+Addition be the palladium salt of 0.006-0.06mol/L, the edetate of 30-100g/L, the ammoniacal liquor of 100-500ml/L; Described reducing agent is N
2H
4, concentration is 0.2-2M; Above-mentioned palladium salt is palladium bichloride, palladium, palladium nitrate or palladium sulfate; Described edetate is disodium ethylene diamine tetraacetate, EDTAP dipotassium ethylene diamine tetraacetate or ethylenediamine tetra-acetic acid two ammoniums.
Plated film also can repeat repeatedly, generally divides and carries out for 2-10 time, upgrades plating bath and before carrier is turned upside down, and is even to guarantee plated film.The temperature of chemical plating is 10-50 ℃
Preliminary treatment of the present invention, surface active and postprocessing working procedures are by prior art operation, and the present invention is the same with other chemical plating process, and the preliminary treatment and the surface active of carrier be there is no specific (special) requirements.It is SnCl that surface active is selected for use relatively commonly used
2/ PdCl
2Method; Or a kind of Pd (OH) of our seminar's invention
2Colloid activation method [Huang Yan, model is lush, Hu Xiaojuan, number of patent application 200710022996.6].
Below the preparation method's of multi-channel type palladium-based composite membrane provided by the present invention concrete steps are once described:
A. the passage cellular ceramic substrate of selecting for use adopts conventional method that the inner surface of carrier passage is activated;
B. as shown in Figure 2, carrier 1 outside after the activation is twined with plastics or elastomeric material, and two ends respectively connect one section silicone rubber tube 2,3, and the lower end of pipe 3 seals and is connected with pipeline 4, latter's source of the gas 7 connects, and is 20-200ml/min by needle valve 5 control nitrogen flows.The mouth of pipe of plating bath 6 (length difference, plating bath amount difference) by silicone rubber tube 2 injected, make all to be full of plating bath 6 in the carrier passage.Because the bubbling effect of bottom gas 7, plating bath 6 has obtained good stirring.Reducing agent 8 adds in the plating bath 6 by pump 9;
C. after a plated film finishes, carrier 1 is reversed, upgrade plating bath 6 and carry out electroless plating reaction.All carrier 1 is put upside down once before each later on renewal plating bath 6, even to guarantee plated film; Also can just finish by a plated film;
D. with the palladium film that makes with the abundant rinsing of deionized water after, use alcohol immersion 20-100min again, at last 100-200 ℃ of dried overnight.
Technical thought proposed by the invention not only is confined to the preparation of Metal Palladium film, also can be used for the preparation of other metal film or alloy film, as Ag, Pt, Cu, Ni film, and Ni-P, Ni-B alloy film etc.The present invention not only can prepare fine and close composite membrane, can also obtain porous composite film, as catalyst.
Here it is emphasized that the related multichannel ceramic monolith of this patent does not comprise the sort of short-thick type carrier that draw ratio is little.Although it is relatively more easy to adopt the present invention to prepare short and thick multi-channel type palladium film, the membrane area that each membrane module can provide is limited, and resistance to mass tranfer is bigger, is difficult to have the coml practical value.
Beneficial effect:
Chemical plating method provided by the invention has solved the preparation difficult problem of multi-channel type palladium-based composite membrane.Electroless plating reaction can at room temperature be carried out, and not only makes operation more convenient, has more reduced the discharging of toxic gas.The present invention has also realized the even growth of rete effectively, has guaranteed the compactness and the adhesive force of palladium film.The conversion ratio of palladium approaches 100% in the plating bath.
Description of drawings:
Fig. 1 is based on the hydrogen separator fundamental diagram of multi-channel type palladium-based composite membrane, and wherein A is a feeding gas, and B is a hydrogen, and C is a tail gas.
Fig. 2 is the used chemical plating appts figure of the present invention, and wherein 1 is the multichannel ceramic monolith, and 2,3,4 is silicone rubber tube, and 5 is needle valve, and 6 is plating bath, and 7 is gas, and 8 is reducing agent, and 9 is peristaltic pump.
Fig. 3 shows the prepared multichannel palladium-based composite membrane photo that goes out of the present invention, and wherein D is the duct, and E is the palladium rete, and F is a carrier layer.
Fig. 4 is the section metallurgical microscopic that shows the prepared multichannel palladium-based composite membrane that goes out of the present invention.
Fig. 5 is the surface electronic micrograph that shows the prepared multichannel palladium-based composite membrane that goes out of the present invention.
The specific embodiment:
Multi-channel type porous ceramics number of active lanes and shape that the present invention was suitable for are not limit, and typical porous ceramic pipe has 7,19,34 passages etc. on the market, and channel shape has circle, hexagon etc.
Embodiment one:
(1). the cellular ceramic substrate average pore size of selecting for use is 0.2 μ m, 19 passages, external diameter 30mm, length is 5cm, passage is rounded, channel diameter 4mm.
(2). the multichannel ceramic monolith is cleaned with commercially available liquid detergent solution, use water rinse then.
(3). adopt conventional SnCl
2/ PdCl
2Method activates the inner surface of passage, and wherein sensitizing solution contains SnCl
22H
2O 5g/L, concentrated hydrochloric acid 1ml/L; Activating solution contains PdCl
20.2g/L, concentrated hydrochloric acid 1ml/L.The carrier outer surface is twined with teflin tape, in sensitizing solution, soak earlier and the water flushing, in activating solution, soak again and the water flushing.After sensitization---the activation processing 5 times, teflin tape is taken apart, be soaked in water 1 hour.
(4). as shown in Figure 2, the electroless plating reaction temperature is 20 ℃.Carrier 1 outside after the activation is twined with teflin tape again, and two ends respectively connect one section silicone rubber tube 2,3, and the lower end sealing of pipe 3 also is connected with pipeline 4, and the latter is connected with the nitrogen steel cylinder, and to control nitrogen flows by needle valve 5 be 60ml/min.The mouth of pipe of 65ml plating bath 6 by silicone rubber tube 2 injected, make all to be full of plating bath 6 in the carrier passage.Consisting of of plating bath 6: PdCl
25g/L, concentrated ammonia liquor 250ml/L, Na
2EDTA 70g/L.Because the bubbling effect of bottom nitrogen 7, plating bath 6 has obtained good stirring.Reducing agent 8 is the N of 0.2mol/L
2H
4Solution, the adding speed of reducing agent is 0.08ml/min, adds in the plating bath 6 by peristaltic pump 9, the palladium ion in plating bath is transformed fully.
(5). carrier 1 is reversed, upgrade plating bath 6 and carry out electroless plating reaction.All carrier 1 is put upside down once before each later on renewal plating bath 6, even to guarantee plated film.
(6). when theoretical calculating palladium film thickness is 6 μ m, stop chemical plating.The palladium film that makes with the abundant rinsing of deionized water, is used soaked in absolute ethyl alcohol half an hour, more at last 120 ℃ of dried overnight.Adopt the air-tightness of radon survey palladium film, under the 1bar pressure, nitrogen flux approaches 0.
Embodiment two:
Mode of operation is with embodiment one, but the cellular ceramic substrate length of selecting for use is 11cm, the consisting of of plating bath: Pd (C
2H
3O
2)
23g/L, concentrated ammonia liquor 150ml/L, K
2EDTA 50g/L.The total use amount of plating bath is 530ml, and prepared palladium film thickness is about 5 μ m.
Embodiment three:
With embodiment one, but the cellular ceramic substrate length of selecting for use is 50cm, and the electroless plating reaction temperature is 35 ℃, and reducing agent is the N of 0.2mol/L
2H
4Solution, gas flow rate are 70ml/min, and reducing agent adding speed is 0.1ml/min, and the bottom bubbled gas is an argon gas, and the total use amount of plating bath is 3000ml, and prepared palladium film thickness is about 6.2 μ m.
Embodiment four:
With embodiment one, but the cellular ceramic substrate length of selecting for use is 20cm, and 37 passages, channel diameter are 40mm, single hole diameter 3.6mm; Reducing agent is the N of 0.5mol/L
2H
4, adding speed is 0.12ml/min; A plated film later stage, the adding speed of reducing agent is 0.5ml/min.The total use amount of plating bath is 1850ml, and prepared palladium film thickness is about 5.5 μ m.
Embodiment five:
With embodiment one, but the cellular ceramic substrate length of selecting for use is 20cm, and 7 passages, channel diameter are 30mm, single hole diameter 6mm.The total use amount of plating bath is 630ml, and prepared palladium film thickness is about 6um.
Above embodiment is used for illustrating the present invention, and the variation of any equivalence of being done under the situation that does not break away from spirit of the present invention all belongs to the scope of claim of the present invention.
Claims (9)
1, a kind of preparation method of multi-channel type hydrogen permeation palladium-based composite membrane, four steps of preliminary treatment, surface active, chemical plating, post processing that comprise carrier, it is characterized in that in the chemical plating step, after multichannel carrier inner surface activates, earlier the leakage that prevents plating bath is wrapped up with plastics or elastomeric material in the carrier outside, then plating bath is placed in the passage of carrier; Reducing agent is added to it in plating bath with pump, the adding speed of reducing agent is controlled at 0.01-5ml/min again; Pass passage by the gas bubbling plating bath is stirred, the bubbled gas flow is 20-200ml/min.
2, preparation method according to claim 1 is characterized in that described multichannel carrier is the multi-channel type ceramic monolith.
3, preparation method according to claim 1 is characterized in that the number of active lanes of described multichannel carrier and shape do not limit, and the length of carrier and diameter ratio are 1-60.
4, preparation method according to claim 1 is characterized in that the length of described multichannel carrier and diameter ratio are 1-30.
5, preparation method according to claim 1 is characterized in that described gas is nitrogen, air, oxygen or argon gas.
6, preparation method according to claim 1, it is characterized in that described palladium plating solution is: with the plating bath cumulative volume is benchmark, Pd
2+Be the palladium salt of 0.006-0.06mol/L, the edetate of 30-100g/L, the ammoniacal liquor of 100-500ml/L; Described reducing agent is N
2H
4, concentration is 0.2-2M.
7, preparation method according to claim 1 is characterized in that described palladium salt is palladium bichloride, palladium, palladium nitrate or palladium sulfate; Described edetate is disodium ethylene diamine tetraacetate, EDTAP dipotassium ethylene diamine tetraacetate or ethylenediamine tetra-acetic acid two ammoniums.
8, preparation method according to claim 1 is characterized in that chemical plating divides 2-10 time, carrier is turned upside down before upgrading plating bath, and is even to guarantee plated film.
9, preparation method according to claim 1, the temperature that it is characterized in that chemical plating is 10-50 ℃.
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Families Citing this family (9)
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| CN101481263B (en) * | 2009-02-26 | 2012-02-15 | 南京工业大学 | Method for preparing supported palladium or palladium alloy membrane |
| CN103157387A (en) * | 2011-12-14 | 2013-06-19 | 南京髙谦功能材料科技有限公司 | Palladium or palladium alloy membrane based on wall-flow honeycomb ceramic and preparation method and application thereof |
| KR101349011B1 (en) * | 2012-01-10 | 2014-01-16 | 한국에너지기술연구원 | Heat resistant hydrogen membrane and manufacturing method thereof |
| CN104178754B (en) * | 2013-05-23 | 2017-02-08 | 中国科学院大连化学物理研究所 | A cyclic chemical plating method for a multi-channel metal palladium composite film |
| CN103768965B (en) * | 2014-01-09 | 2015-12-30 | 南京工业大学 | A kind of preparation method of multichannel mixed conductor hollow-fibre membrane |
| CN105039944B (en) * | 2015-09-15 | 2017-10-13 | 南京工业大学 | The preparation of palladium or palladium alloy membrane component |
| AT15435U1 (en) * | 2016-06-22 | 2017-08-15 | Plansee Se | diaphragm assembly |
| CN108014648A (en) * | 2016-10-31 | 2018-05-11 | 中国科学院大连化学物理研究所 | A kind of method for preparing double-deck palladium-based composite membrane |
| CN107585741B (en) * | 2017-09-30 | 2020-04-24 | 西北有色金属研究院 | Ultra-high purity hydrogen separator |
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