CN104176707A - Method for purifying hydrogen from sulfur-containing gas mixture - Google Patents
Method for purifying hydrogen from sulfur-containing gas mixture Download PDFInfo
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- CN104176707A CN104176707A CN201310196590.5A CN201310196590A CN104176707A CN 104176707 A CN104176707 A CN 104176707A CN 201310196590 A CN201310196590 A CN 201310196590A CN 104176707 A CN104176707 A CN 104176707A
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Abstract
The invention provides a method using a palladium alloy composite membrane for separating hydrogen from a sulfur-containing gas mixture; according to the method, a chemical plating method is used, the palladium alloy composite membrane is used for separating the sulfur-containing gas mixture with the H2S content of 0.5-20ppm. Under the separation pressure of 0.2-1.0MPa and at the separation temperature of 300 to 500 Deg. C, the separated hydrogen purity is more than 99%. At the same time the palladium alloy composite film reflects the better sulfur resistant characteristic, compared with a pure palladium metal film, the palladium alloy composite film can be used for the treatment of the sulfur-containing gas mixture in industry, and has a good application prospect.
Description
Technical field:
The present invention relates to a kind of palladium alloy composite membrane that utilizes from the method for sulfur-bearing mixed gas separation hydrogen.Specifically provide a kind of and utilized the high palladium alloy composite membrane of amount thoroughly from the synthetic gas of the H2S containing different concns, the separated method that obtains hydrogen under all temps pressure.Will be to various sulfur-bearing synthetic gas in industry, and similarly the separation of sulfur-bearing mixed air obtains widespread use.
Background technology
Hydrogen is as a kind of excellent carrier of clean energy, and its preparation, separation and storage have become study hotspot in recent years.And compact metal palladium film has very high hydrogen permeation selectivity and rate of permeation, in research fields such as Hydrogen Separation purifying and membrane reactors, receive much attention.The process that H2 sees through Pd alloy film comprise hydrogen molecule film surface dissociate and absorption, the gap of hydrogen atom at metal between diffusion and at film the other end hydrogen atom desorption with form hydrogen, this i.e. so-called " dissolving-diffusion " process.It has been generally acknowledged that, the diffusion of hydrogen atom is the control step that determines saturating hydrogen speed.But along with the progress of film preparation technique, at present alloy film can be as thin as several microns even below micron, and this can not only improve permeation flux, also can effectively reduce costs, very favourable to its industrial application.Film thickness reduction must cause surface dissociation adsorption process to produce impact more significantly to saturating hydrogen speed, and this point is proved by experimental result
Yet foreign gas, especially S-contained substance very easily cause palladium metal sulfuration and inactivation, and the membrane poisoning that sulfide strong adsorption causes on metallic palladium surface, is permanent.If sulfide for example, in the excessive concentration (sulfide surface fraction of coverage is greater than 0.5 individual layer) on palladium film surface, palladium film surface may form PdSx compound, cause the saturating hydrogen performance of palladium film to completely lose.Research shows not only likely to improve antitoxin performance by adding another kind of metal to form alloy film, can also stop the generation of Hydrogen Brittleness Phenomena, and obtain the hydrogen rate of permeation higher than pure palladium film.How promoting the antitoxin performance of metallic membrane and don't significantly reduce the rate of permeation of hydrogen, is the major issue in palladium alloy membrane design.A lot of researchists invest sight palladium-based composite membrane and the palladium alloy composite membrane that has propping material, as palladium-silver, palladium copper composite membrane etc.Compare with silver, adding of copper further reduces palladium film production cost, and oxygen flux is but suitable with it; And palladium-copper alloy has more opposing sulfide poisoning ability, and hydrogen sulfide modal foreign gas in hydrogen sepn process just, so the preparation of palladium-copper alloy composite membrane, character, application become study hotspot.
Summary of the invention
The present invention is in order to make up the pure palladium film of metal poor deficiency of sulfur resistance in purifying hydrogen of hydrogen application, adopt the high palladium alloy composite membrane of amount thoroughly under certain separating pressure, separation temperature, synthetic gas H2S content is at 0.5～20ppm, and separation obtains purity at more than 99% hydrogen.
In order to realize present method, adopt chemical plating method, utilize the electroless plating time to control, the height that is prepared into definite composition is measured palladium alloy composite membrane thoroughly.Comprise the following steps:
1) adopt chemical plating method, be prepared into the high palladium-copper alloy of amount thoroughly, polarium, porpezite copper alloy composite membrane.
2), at 500 ℃, under H2 atmosphere, palladium alloy composite membrane is carried out to alloying and activation.
3), at separating pressure 0.2～0.6MPa, under 300 ℃～500 ℃ conditions of separation temperature, utilize gas flow controller will consist of H270%～90%, N210%～30%, H2S
The mixed air of (0.5～20ppm) (all making scope into) passes into palladium alloy composite membrane separator.4) at separating pressure 0.2～0.6MPa, under 300 ℃～500 ℃ conditions of separation temperature, utilize gas flow controller and water pump will consist of H220%～60%, H2O20%～40%, CO220%～50%, CO1%～10%, N21%～5%, H2S(0.5～20ppm) synthetic gas pass into palladium alloy composite membrane separator.
5) hydrogen selective ground, by palladium alloy composite membrane, obtains hydrogen in per-meate side.
The weight of the high polarium of amount thoroughly composite membrane consists of Pd:70%～90%, Au:10%～30%;
Or the weight of the high palladium-copper alloy of amount thoroughly composite membrane consists of Pd:70%～90%, CU:10%～30%;
Or the weight of the high porpezite of amount thoroughly copper alloy composite membrane consists of Pd:70%～90%, CU:10%～30%, Au:10%～30%.
The preparation process of the high palladium alloy composite membrane of amount thoroughly comprises: the 1) cleaning of matrix: first utilize mass concentration 2%～6%KOH or NaOH solution to clean, then with dehydrated alcohol, matrix is cleaned, then with deionized water, pH value is washed till to 6.5～7.5; 2) sensitization of matrix activation: matrix is first at 1～5g/L SnCl
2in solution, soak, then put into 1～5g/L PdCl
2in solution, become nuclear reaction, the Pd forming on surface checks electroless plating and plays katalysis; 3) electroless plating of metallic membrane: the matrix after activation is put into palladium plating solution and form palladium film; 4) alloy plating film: the palladium film having plated is put into copper electrolyte or golden plating solution, control alloy composition by the period; 5) dry through alloy film, in 400 ℃～600 ℃ hydrogen atmosphere interalloies and reduction.
A kind of palladium alloy composite membrane that utilizes of the present invention, from the method for sulfur-bearing mixed air separating hydrogen gas, adopts chemical plating method, is prepared into the high palladium alloy composite membrane of amount thoroughly, and the mixed air that palladium alloy composite membrane is applied to sulfur-bearing is separated, and H2S content is 0.5～20ppm.At separating pressure 0.2～1.0MPa, at 300 ℃～500 ℃ of separation temperatures, isolate hydrogen purity and reach more than 99%.Palladium alloy composite membrane has embodied good anti-sulphur property simultaneously, with respect to pure metallic palladium film, can be used for the processing of industrial sulfur-bearing gas mixture, has good application prospect.
Accompanying drawing explanation
Fig. 1 Experimental equipment; 1 is nitrogen sweep gas, and 2 is pure hydrogen infiltration gas, and 3 is synthetic gas, and 4 is copper palladium alloy membrane, and 5 is thermopair, and 6 is process furnace, and 7 is separated tail gas.
Hydrogen quantitative change thoroughly in the alloying of Fig. 2 palladium-copper alloy film and reactivation process;
The impact of Fig. 3 temperature on palladium-copper alloy film purifying hydrogen of hydrogen result from sulfur-bearing nitrogen hydrogen mixed air;
The impact of Fig. 4 pressure on palladium-copper alloy film purifying hydrogen of hydrogen result from sulfur-bearing nitrogen hydrogen mixed air;
The impact of Fig. 5 H2S content on palladium-copper alloy film purifying hydrogen of hydrogen result from sulfur-bearing nitrogen hydrogen mixed air;
In the stability experiment of Fig. 6 palladium-copper alloy film purifying hydrogen of hydrogen from sulfur-bearing synthetic gas, hydrogen flowing quantity and purity are over time.
Embodiment
The technology of the present invention details is by following embodiment detailed description in addition.It should be noted that lifted embodiment, its effect just further illustrates technical characterictic of the present invention, rather than limits the present invention.
Embodiment 1:
Adopt porous ceramics as matrix, utilize mass concentration 4%NaOH solution and ethanol to clean matrix, then with deionized water, pH value is washed till and approaches 7.Matrix is at SnCl
2solution soaking, then put into PdCl
2in solution, become nuclear reaction, the matrix after activation is put into palladium plating solution and form palladium film, the palladium film having plated is put into copper electrolyte, form alloy film.Palladium plating solution consists of: PdCl
2: 2g/L; NH
3h
2o:9.8g/L; N
2h
4: 300mg/L; EDTA:14.92g/L.Copper electrolyte consists of: Cu (NO
3)
23H
2o:9.6g/L; Na
2eDTA:29.8g/L; 2,2-bipyridyl:20mg/L; K4[Fe (CN) 6] 3H
2o50mg/L; NaOH:11g/L; HCHO (>=36.5%) 125mL/L.Utilize the electroless plating time to control, be prepared into the height that consists of Pd72.9Cu27.1 and thoroughly measure palladium-copper alloy composite membrane, by weighting method, recording thickness is 3.2 μ m.Pack reactor into, at 500 ℃, H
2in atmosphere, under 0.1MPa pressure, palladium-copper alloy composite membrane is carried out to alloying and activation.At set intervals the hydrogen flowing quantity of per-meate side is measured, when hydrogen flowing quantity keeps, after stable no longer variation, showing that the alloying of palladium-copper alloy film and activation complete.See Fig. 2.
Embodiment 2
Adopt chemical plating method, utilize the electroless plating time to control, adopt porous ceramics as matrix, utilize mass concentration 4%NaOH solution and ethanol to clean matrix, then with deionized water, pH value is washed till and approaches 7.Matrix is at SnCl
2solution soaking, then put into PdCl
2in solution, become nuclear reaction, the matrix after activation is put into palladium plating solution and form palladium film, the palladium film having plated is put into copper electrolyte, form alloy film.Palladium plating solution consists of: PdCl
2: 2g/L; NH
3h
2o:9.8g/L; N
2h
4: 300mg/L; EDTA:14.92g/L.Copper electrolyte consists of: Cu (NO
3)
23H
2o:9.6g/L; Na
2eDTA:29.8g/L; 2,2-bipyridyl:20mg/L; K4[Fe (CN) 6] 3H
2o50mg/L; NaOH:11g/L; HCHO (>=36.5%) 125mL/L.Be prepared into the height that consists of Pd79.1Cu20.9 and thoroughly measure palladium-copper alloy composite membrane, by weighting method, recording thickness is 4.1 μ m.As example 1 method is carried out alloying and activation.
1) under 300 ℃～500 ℃ conditions of separating pressure, pressure is 0.6MPa, utilizes gas flow controller will consist of H290%, N210%, H
2the mixed air of S20ppm passes into palladium-copper alloy composite membrane separator, and charge flow rate is 3000ml/min, investigates temperature condition for the impact of Reaction Separation: experimental result is shown in Fig. 3.
2) under 400 ℃ of conditions of separation temperature, pressure is 0.2～0.6MPa, utilizes gas flow controller will consist of H290%, N210%, H
2the mixed air of S20ppm passes into palladium-copper alloy composite membrane separator, and charge flow rate is 3000ml/min, investigates temperature condition for the impact of Reaction Separation: experimental result is shown in Fig. 4.
3) under 400 ℃ of conditions of separating pressure, pressure is 0.6MPa, utilizes gas flow controller will consist of H
290%, N
210%, H
2the mixed air of S0.5～20ppm passes into palladium-copper alloy composite membrane separator, and charge flow rate is 3000ml/min, investigates H2S condition for the impact of Reaction Separation: experimental result is shown in Fig. 5.
Brief summary: at copper alloy composite membrane separator to containing H
2in the sepn process of S mixed air, the hydrogen flowing quantity that separation obtains is along with temperature, the rising of pressure and increasing, and hydrogen purity also increases thereupon.And along with the lifting of the content of H2S in mixed air, the hydrogen flowing quantity that separation obtains slightly declines, hydrogen purity also declines thereupon.In all conditions test, the hydrogen purity that separation obtains, more than 99%, illustrates that copper alloy composite membrane has kept certain selectivity.
Example 3:
Adopt chemical plating method, adopt porous ceramics as matrix, utilize mass concentration 4%NaOH solution and ethanol to clean matrix, then with deionized water, pH value is washed till and approaches 7.Matrix is at SnCl
2solution soaking, then put into PdCl
2in solution, become nuclear reaction, the matrix after activation is put into palladium plating solution and form palladium film, the palladium film having plated is put into copper electrolyte, form alloy film.Palladium plating solution consists of: PdCl
2: 2g/L; NH
3h
2o:9.8g/L; N
2h
4: 300mg/L; EDTA:14.92g/L.Copper electrolyte consists of: Cu (NO
3)
23H
2o:9.6g/L; Na
2eDTA:29.8g/L; 2,2-bipyridyl:20mg/L; K4[Fe (CN) 6] 3H
2o50mg/L; NaOH:11g/L; HCHO (>=36.5%) 125mL/L.Utilize the electroless plating time to control, be prepared into the height that consists of Pd79.1Cu20.9 and thoroughly measure palladium-copper alloy composite membrane, by weighting method, recording thickness is 4.1 μ m.As example 1 method is carried out alloying and activation.At separating pressure 0.6MPa, under 450 ℃ of conditions of separation temperature, utilize gas flow controller and water pump H234%, H2O37%, CO223%, CO5%, N21%, H
2the synthetic gas of S5ppm passes into palladium-copper alloy composite membrane separator, and charge flow rate is 400ml/min, in per-meate side, adds the nitrogen of 100ml/min as sweep gas, palladium-copper alloy composite membrane is carried out to study on the stability: experimental result is shown in Fig. 6.
In between the probation of stability, within first 100 hours, hydrogen flowing quantity declines to some extent, but after sepn process in, hydrogen flowing quantity tends towards stability, hydrogen purity slow decreasing, but remain on more than 97%, and lowering speed eases up.Palladium-copper alloy composite membrane is containing H
2in the synthetic gas separation of S, shown good anti-sulphur property.
Claims (9)
1. a method for purifying hydrogen of hydrogen from sulfur-bearing mixed air, is characterized in that: under certain separating pressure, separation temperature, sulfur-bearing gas mixture is passed into the high palladium alloy composite membrane of amount thoroughly, can obtain purity at more than 99% hydrogen after separation.
2. it is characterized in that in accordance with the method for claim 1: described palladium alloy membrane is palladium-copper alloy, polarium or porpezite copper alloy composite membrane.
3. according to the method described in claim 1 or 2, it is characterized in that: the thickness of the high palladium alloy composite membrane of amount is thoroughly 1～10 μ m.
4. according to the method described in claim 1,2 or 3, it is characterized in that:
The weight of the high polarium of amount thoroughly composite membrane consists of Pd:70%～90%, Au:10%～30%;
Or the weight of the high palladium-copper alloy of amount thoroughly composite membrane consists of Pd:70%～90%, CU:10%～30%;
Or the weight of the high porpezite of amount thoroughly copper alloy composite membrane consists of Pd:70%～90%, CU:10%～30%, Au:10%～30%.
5. in accordance with the method for claim 1, it is characterized in that: separating pressure 0.2～1.0MPa, 300 ℃～500 ℃ of separation temperatures.
6. in accordance with the method for claim 1, it is characterized in that: mixed hydrogen and nitrogen or the synthetic gas of the sulfur-bearing that separated mixed air is, in separated mixed air, sulphur is H
2s.
7. according to the method described in claim 1 or 6, it is characterized in that: sulphur content is 0.5～20ppm.
8. it is characterized in that in accordance with the method for claim 6: the volume of hydrogen nitrogen mixed gas consists of: H
270%～90%, N
210%～30%;
Synthetic gas volume consists of H
220%～60%, H
2o20%～60%, CO
218%～50%, CO1%～10%, N
21%～5%.
9. according to the method described in claim 1 or 2, it is characterized in that:
The preparation process of the high palladium alloy composite membrane of amount thoroughly comprises: the 1) cleaning of matrix: first utilize mass concentration 2%～6%KOH or NaOH solution to clean, then with dehydrated alcohol, matrix is cleaned, then with deionized water, pH value is washed till to 6.5～7.5; 2) sensitization of matrix activation: matrix is first at 1～5g/L SnCl
2in solution, soak, then put into 1～5g/L PdCl
2in solution, become nuclear reaction, the Pd forming on surface checks electroless plating and plays katalysis; 3) electroless plating of metallic membrane: the matrix after activation is put into palladium plating solution and form palladium film; 4) alloy plating film: the palladium film having plated is put into copper electrolyte or golden plating solution, control alloy composition by the period; 5) dry through alloy film, in 400 ℃～600 ℃ hydrogen atmosphere interalloies and reduction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492279A (en) * | 2014-12-24 | 2015-04-08 | 沈阳工程学院 | Method for preparing sulfur resistant palladium composite membrane by separating hydrogen from synthesis gas from coal |
| CN108079797A (en) * | 2018-01-02 | 2018-05-29 | 兰州理工大学 | A kind of preparation method of hydrogen palladium alloy composite membrane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555594A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院大连化学物理研究所 | Preparation method for forming controllable palladium alloy composite film |
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2013
- 2013-05-23 CN CN201310196590.5A patent/CN104176707A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555594A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院大连化学物理研究所 | Preparation method for forming controllable palladium alloy composite film |
Non-Patent Citations (3)
| Title |
|---|
| NATALIE POMERANTZ ET AL.: "Effect of H2S on the Performance and Long-Term Stability of Pd/Cu Membranes", 《IND.ENG.CHEM.RES》, vol. 48, 23 March 2009 (2009-03-23), pages 4030 - 4039 * |
| T.A.PETERS ET AL.: "Hydrogen transport through a selection of thin Pd-alloy membranes: stability, H2S inhibition, and flux recovery in hydrogen and simulated WGS mixtures", 《CATALYSIS TODAY》, vol. 193, 31 January 2012 (2012-01-31), pages 8 - 19 * |
| 王学松: "《气体膜技术》", 30 June 2010, article "钯合金膜的制备方法", pages: 226 - 228 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492279A (en) * | 2014-12-24 | 2015-04-08 | 沈阳工程学院 | Method for preparing sulfur resistant palladium composite membrane by separating hydrogen from synthesis gas from coal |
| CN108079797A (en) * | 2018-01-02 | 2018-05-29 | 兰州理工大学 | A kind of preparation method of hydrogen palladium alloy composite membrane |
| CN108079797B (en) * | 2018-01-02 | 2020-11-03 | 兰州理工大学 | Preparation method of hydrogen-permeable palladium alloy composite membrane |
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Application publication date: 20141203 |