CN109778152A - A kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer - Google Patents
A kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer Download PDFInfo
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- CN109778152A CN109778152A CN201711104451.XA CN201711104451A CN109778152A CN 109778152 A CN109778152 A CN 109778152A CN 201711104451 A CN201711104451 A CN 201711104451A CN 109778152 A CN109778152 A CN 109778152A
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Abstract
The present invention relates to a kind of improvement chemical plating methods of high-specific surface area palladium/composite membrane of polymer.Polymer film surface is subjected to hydrophilic treated before progress chemical plating, and a certain amount of surfactant is added into plating solution in plating process, to reduce plating solution surface tension, promote infiltration of the palladium plating solution in duct, and then obtains fine and close flawless palladium/composite membrane of polymer.This method is easy to operate, and process is easily-controllable, is able to achieve Metal Palladium or the zero defect preparation of its alloy composite film, and significantly improve the binding force and stability of metal film and polymeric matrix, is suitable for scale industrial production.
Description
Technical field
The present invention relates to a kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer, by Metal Palladium or its
Alloy film is by electroless plating technology in polymer fiber film (including cellulose acetate (CA), Kynoar (PVDF), poly- four
Vinyl fluoride (PTFE) or polysulfones (PSF) etc.) surface formation dense film, it can be used for the separation, purifying and production of hydrogen.
Background technique
Hydrogen Energy is generally acknowledged clean energy resource, is being shown one's talent as low-carbon and the zero carbon energy.21 century, China and beauty
State, Japan, Canada, European Union etc. have all formulated Hydrogen Energy development plan.How a large amount of and cheap studying in countries in the world
Produce hydrogen.Currently, plant hydrogen passes through natural gas, coal and lighter hydrocarbons production Gas Mixtures Containing Hydrogen (75~80%H first2), then
It is separated by cryogenic separation or pressure-variable adsorption, hydrogen is purified, however cryogenic separation and PSA Technology all have
Energy consumption height and the big disadvantage of plant investment.
Palladium membrane technology is considered to be the most potential technology for realizing high-purity hydrogen production.Palladium film is dissolved with unique hydrogen
Ability and by dissolution-diffusion mechanism penetrate hydrogen, so that hydrogen selective infinitely great on realization theory and high hydrogen are saturating
Amount.With conventional hydrogen isolation technics such as pressure swing adsorption method, Deep Cooling Method etc. is compared, palladium membrane separation technique have land occupation less, small investment,
Low energy consumption and it is easy to operate the advantages that.As traditional metal palladium tube has been used for providing 99.99999% or more for semiconductor
Ultra-pure hydrogen.But due to the requirement of application intensity, the thickness of metal palladium tube at least wants 100-200 microns, this is not only consumed largely
Precious metal palladium, and make its permeated hydrogen amount very low, plant investment is extremely expensive, separating energy consumption is very high, hydrogen manufacturing cost and system
Hydrogen scale is unable to satisfy the demand of the following scale application.Metal Palladium film is supported and porous counterdie such as stainless steel or ceramic monolith
On, metal palladium-based composite membrane can be prepared, thickness can be reduced to several microns, compared with metal palladium tube, significantly improve hydrogen
It measures while substantially reducing cost.
The present invention provides a kind of using chemically plating for high-specific surface area palladium/composite membrane of polymer method, by right
Polymer film surface carries out hydrophilic treated and the mode of surfactant is added into chemical plating fluid, promotes palladium plating solution in duct
In infiltration, and then obtain fine and close flawless palladium-based composite membrane.Compared with existing stainless steel or single channel ceramics counterdie, polymerization
Object counterdie can significantly reduce cost, and significantly improve palladium-based composite membrane area/volume ratio (see attached drawing 1).It is computed, polymer fiber
The area/volume ratio of (outer diameter 1-2mm) load palladium-based composite membrane can reach 6000m2/m3, and traditional stainless steel or single channel ceramics
The area/volume ratio that (outer diameter 10-12mm) loads palladium-based composite membrane is only 45m2/m3。
Summary of the invention
The present invention relates to a kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer, by Metal Palladium or its
Alloy film is by electroless plating technology in polymer fiber film (including cellulose acetate (CA), Kynoar (PVDF), poly- four
Vinyl fluoride (PTFE) or polysulfones (PSF) etc.) surface formation dense film, it can be used for the separation, purifying and production of hydrogen.By to poly-
Compound film surface carries out hydrophilic treated and the mode of surfactant is added into chemical plating fluid, promotes palladium plating solution in duct
Infiltration, and then obtain fine and close flawless palladium-based composite membrane.
It is that the present invention uses the specific technical proposal is: carrying out chemical plating before polymer film surface is subjected to hydrophilic treated,
A certain amount of surfactant is added in plating process into plating solution, to reduce plating solution surface tension, promotes palladium plating solution in hole
Infiltration in road, and then obtain fine and close flawless palladium-based composite membrane.
(1) hydrophilic treated is carried out to polymer film surface before chemical plating, is such as impregnated with deionized water, 2) ultrasonic treatment, or
3) using the methods of polymer treatment liquid such as sodium-naphthalene complex compound/tetrahydrofuran (THF) solution processing；
(2) in plating process, the mode of surfactant is added into plating solution, promotes infiltration of the palladium plating solution in duct
Thoroughly, and then fine and close flawless palladium-based composite membrane is obtained.Surfactant used includes lauryl sodium sulfate (SDS) or fat
Acid glyceride or sucrose ester etc..
The utility model has the advantages that
(1) improved electroless plating technology has effectively facilitated infiltration of the plating solution in polymer duct, can be used to prepare zero and lack
Sunken fine and close palladium-based composite membrane, and have good permeated hydrogen amount and selectivity, in addition preparation process is simple, easily controllable, is suitble to use
In scale industrial production.
(2) the Polymer-supported palladium-based composite membrane material has high-specific surface area, compact-sized and low-cost obvious excellent
Point has the fields such as hydrogen, separation and production to have preferable application prospect.
Detailed description of the invention
Fig. 1: conventional one-channel ceramic load palladium-based composite membrane (outer diameter 10-12mm) (a) and polymer fiber (outer diameter 1-2mm)
It loads palladium-based composite membrane (b).
Fig. 2: the scanning electron microscope (SEM) photograph of polytetrafluoroethylene (PTFE) (PTFE) load palladium-based composite membrane prepared by embodiment 1；(a) surface (b)
Cross section.
This method is easy to operate, and process is easily-controllable, is able to achieve Metal Palladium or the zero defect preparation of its alloy composite film, and significant
The binding force and stability of metal film and polymeric matrix are improved, scale industrial production is suitable for.
Specific embodiment
Embodiment 1
Polymeric film material used is polytetrafluoroethylene (PTFE) (PTFE), is fine and close knot after the progress high temperature sintering processing of fiber both ends
Structure (both ends length is respectively 15cm), sintering temperature are 400 DEG C, time 2min.Middle section porous part length is 10cm, outside
Diameter/internal diameter is respectively 2mm and 1mm, and pore size is 0.1 μm.
(1) hydrophilic treated of PTFE counterdie
PTFE counterdie is put into deionized water and impregnates 2h, promotes infiltration of the deionized water in duct.
(2) preparation and performance test of palladium-based composite membrane
It activates and is sensitized including a. carrier surface, b. chemical plating and c. post-process three steps
A. carrier surface activation sensitization: by the PTFE counterdie after hydrophilic treated respectively in SnCl2Sensitization in solution (6g/L)
And rinsed with deionized water, in PdCl2It activates in solution (0.4g/L) and is rinsed with deionized water, repeated sensitization-activation 5 times
Afterwards, it is cleaned under vacuumized conditions with deionized water.
B. chemical plating: after the activated sensitization in the outer surface PTFE, being placed in plating solution and carry out chemical plating, until reaching required
1.2 μm of film thickness (see attached drawing 2).Chemical plating fluid composition are as follows:
[Pd(NH3)2]Cl2(1g/L),EDTA·2Na(90g/L),NH2-NH2·H2O(0.2g/L),NH3·H2O (28%)
(100ml/L), wherein Surfactant SDS
(SDS) volume content is 1%, PH=9, and chemical plating temperature is 55 DEG C.
C. post-process: be sealed using palladium-based composite membrane of the epoxy resin to above-mentioned preparation, after in nitrogen or helium atmosphere
Under from room temperature by the temperature program of 1 DEG C/min be warming up to 250 DEG C, in Pfeed/PpermUnder the conditions of=2/1bar, nitrogen and hydrogen are carried out
The measurement of permeability to gas.Measuring hydrogen rate is 8.0E-7mol/m2.s.Pa,H2/N2Gas selectivity reaches 10240.
Embodiment 2
Polymeric film material used is Kynoar (PVDF), is fine and close knot after the progress high temperature sintering processing of fiber both ends
Structure (both ends length is respectively 15cm), sintering temperature are 250 DEG C, time 2min.Middle section porous part length is 10cm, caliber
Specification is 2mm × 1mm, and aperture is 0.2 μm.
(1) hydrophilic treated of PVDF counterdie
PVDF counterdie is placed in deionized water, and with ultrasonic treatment 1h.
(3) preparation and performance test of palladium-based composite membrane
It activates and is sensitized including a. carrier surface, b. chemical plating and c. post-process three steps
A. carrier surface activation sensitization: by the PTFE counterdie after hydrophilic treated respectively in SnCl2Sensitization in solution (6g/L)
And rinsed with deionized water, in PdCl2It activates in solution (0.4g/L) and is rinsed with deionized water, repeated sensitization-activation 5 times
Afterwards, it is cleaned under vacuumized conditions with deionized water.
B. chemical plating: after the activated sensitization in the outer surface PVDF, being placed in plating solution and carry out chemical plating, until reaching required
3 μm of film thickness.Chemical plating fluid composition are as follows: [Pd (NH3)2]Cl2(1g/L),EDTA·2Na(90g/L),NH2-NH2·H2O(0.2g/
L),NH3·H2O (28%) (100ml/L), wherein the volume content of Surfactant SDS (SDS) is 1%, PH
=9, chemical plating temperature is 55 DEG C.
C. post-process: be sealed using palladium-based composite membrane of the epoxy resin to above-mentioned preparation, after in nitrogen or helium atmosphere
Under from room temperature by the temperature program of 1 DEG C/min be warming up to 150 DEG C, in Pfeed/PpermUnder the conditions of=2/1bar, nitrogen and hydrogen are carried out
The measurement of permeability to gas.Measuring hydrogen rate is 3.3E-7mol/m2.s.Pa,H2/N2Gas selectivity reaches 10250.
Embodiment 3
Polymeric film material used is polytetrafluoroethylene (PTFE) (PTFE), is fine and close knot after the progress high temperature sintering processing of fiber both ends
Structure (both ends length is respectively 10cm), sintering temperature are 400 DEG C, time 2min.Middle section porous part length is 5cm, caliber
Specification is 2mm × 1mm, and aperture is 0.5 μm.
(1) hydrophilic treated of PTFE counterdie
A. PTFE counterdie is impregnated into 5h in sodium-naphthalene complex compound/tetrahydrofuran (THF) solution that concentration is 0.6mol/L.
B. by PTFE counterdie using being rinsed in deionized water, until surface becomes white again.
(4) preparation and performance test of palladium-based composite membrane
It activates and is sensitized including a. carrier surface, b. chemical plating and c. post-process three steps
A. carrier surface activation sensitization: by the PSF counterdie after hydrophilic treated respectively in SnCl2It is sensitized simultaneously in solution (6g/L)
It is rinsed with deionized water, in PdCl2It activates in solution (0.4g/L) and is rinsed with deionized water, after repeating sensitization-activation 5 times,
It is cleaned under vacuumized conditions with deionized water.
B. chemical plating: after the activated sensitization in the outer surface PTFE, being placed in plating solution and carry out chemical plating, until reaching required
3 μm of film thickness.Chemical plating fluid composition are as follows: [Pd (NH3)2]Cl2(1g/L),EDTA·2Na(90g/L),NH2-NH2·H2O(0.2g/
L),NH3·H2O (28%) (100ml/L), wherein the volume content of surfactant fatty acid glyceride be 0.5%, PH=9,
Chemical plating temperature is 55 DEG C.
C. post-process: be sealed using palladium-based composite membrane of the epoxy resin to above-mentioned preparation, after in nitrogen or helium atmosphere
Under from room temperature by the temperature program of 1 DEG C/min be warming up to 250 DEG C, in Pfeed/PpermUnder the conditions of=2/1bar, nitrogen and hydrogen are carried out
The measurement of permeability to gas.Measuring hydrogen rate is 9.3E-7mol/m2.s.Pa,H2/N2Gas selectivity reaches 8360.
Claims (8)
1. a kind of improvement chemical plating method of high-specific surface area palladium/composite membrane of polymer material, it is characterised in that: 1) carry out chemistry
Polymer film surface is subjected to hydrophilic treated before plating, 2) chemical plating is carried out in the plating solution added with surfactant.
2. the method as described in claim 1, it is characterised in that: polymeric fibre material pore size used 0.1-1 μm it
Between, for outer diameter between 0.5-5mm, polymer material can be cellulose acetate (CA), Kynoar (PVDF), polytetrafluoro
One of ethylene (PTFE) or polysulfones (PSF) etc. or two kinds or more.
3. the method as described in claim 1, it is characterised in that: the method for the polymer film surface hydrophilic treated includes following
One of or two kinds or more, 1) with deionized water impregnate 1h or more, 2) be ultrasonically treated and 1h or more or 3) make in deionized water
With polymer treatment liquid such as sodium-naphthalene complex compound/tetrahydrofuran (THF) solution (concentration 0.5mol/L-2mol/L) processing 1h with
It is washed after upper.
4. the method as described in claim 1, it is characterised in that: in the plating solution of the chemical plating method, palladium reagent is Pd
(NO3)2,PdSO4, or PdCl2One of or two kinds or more, the concentration of palladium reagent is 0.1mol/L~10mol/L；Reducing agent
It is SnCl2, one of hydrazine or sodium formate or two kinds or more, the concentration of reducing agent is 0.1mol/L~10mol/L；Into plating solution
0.2-1.5 is addedvol.% or so surfactant, surfactant are lauryl sodium sulfate (SDS) or fatty glyceride
Or one of sucrose ester or two kinds or more.
5. method as described in claim 1 or 4, it is characterised in that: also added with the palladium removing for forming palldium alloy in the plating solution
Except the other metal salts of solubility, be prepared into palladium alloy membrane；Other metals are one of copper, silver etc. or two kinds or more, yin
Ion is one of nitrate anion, sulfate radical, chloride ion or two kinds or more.
6. the method as described in claim 1,4 or 5, it is characterised in that: also add NH in the plating solution2-NH2·H2O(0.1-
0.5g/L),NH3·H2O (20-30%) (50-200ml/L), PH=8-11.
7. the method as described in claim 1,4,5 or 6, it is characterised in that: chemical plating temperature is anti-every time between 35-60 DEG C
It is 1-3h between seasonable, number of repetition is 2-15 times.
8. the method as described in claim 1,4,5,6 or 7, it is characterised in that: the thickness of Metal Palladium or its alloy film is 0.5~
20μm。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919409A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Metal membrane separator and application |
Citations (5)
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|---|---|---|---|---|
| US4720400A (en) * | 1983-03-18 | 1988-01-19 | W. L. Gore & Associates, Inc. | Microporous metal-plated polytetrafluoroethylene articles and method of manufacture |
| CN1481448A (en) * | 2001-03-06 | 2004-03-10 | О | Plating method of metal film on surface of polymer |
| CN101195911A (en) * | 2006-12-08 | 2008-06-11 | 埃托特克德国有限公司 | Preprocessing solution and method for forming coating metal layer on substrate with plastic surface |
| CN101302612A (en) * | 2006-05-11 | 2008-11-12 | 日立麦克赛尔株式会社 | Manufacturing method of polymer member and polymer member |
| CN104178754A (en) * | 2013-05-23 | 2014-12-03 | 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 |
-
2017
- 2017-11-10 CN CN201711104451.XA patent/CN109778152A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720400A (en) * | 1983-03-18 | 1988-01-19 | W. L. Gore & Associates, Inc. | Microporous metal-plated polytetrafluoroethylene articles and method of manufacture |
| CN1481448A (en) * | 2001-03-06 | 2004-03-10 | О | Plating method of metal film on surface of polymer |
| CN101302612A (en) * | 2006-05-11 | 2008-11-12 | 日立麦克赛尔株式会社 | Manufacturing method of polymer member and polymer member |
| CN101195911A (en) * | 2006-12-08 | 2008-06-11 | 埃托特克德国有限公司 | Preprocessing solution and method for forming coating metal layer on substrate with plastic surface |
| CN104178754A (en) * | 2013-05-23 | 2014-12-03 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 唐金晶: "钯/聚合物基复合膜的制备、表征及性能研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919409A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Metal membrane separator and application |
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